Picolinamides As Fungicides

Abstract

This disclosure relates to picolinamides of Formula I and their use as fungicides. ##STR00001##

Description

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority under 35 U.S.C. .sctn. 119 of U.S. provisional patent application Ser. No. 62/442,904 filed Jan. 5, 2017, which application is hereby incorporated by reference in its entirety.

BACKGROUND & SUMMARY

[0002] Fungicides are compounds, of natural or synthetic origin, which act to protect and/or cure plants against damage caused by agriculturally relevant fungi. Generally, no single fungicide is useful in all situations. Consequently, research is ongoing to produce fungicides that may have better performance, are easier to use, and cost less.

[0003] The present disclosure relates to picolinamides and their use as fungicides. The compounds of the present disclosure may offer protection against ascomycetes, basidiomycetes, deuteromycetes and oomycetes.

[0004] One embodiment of the present disclosure may include compounds of Formula I:

##STR00002##

[0005] wherein:

[0006] X is hydrogen or C(O)R.sub.5;

[0007] Y is hydrogen, C(O)R.sub.5, or Q;

[0008] Q is

##STR00003##

[0009] wherein Z is N or N.sup.+.fwdarw.O.sup.- and W is O or S;

[0010] R.sub.1 is hydrogen or alkyl, substituted with 0, 1 or multiple R.sub.8;

[0011] R.sub.2 is methyl;

[0012] R.sub.3 and R.sub.3' are independently chosen from C.sub.2-C.sub.6 alkyl, C.sub.3-C.sub.6 cycloalkyl, aryl or heteroaryl, each optionally substituted with 0, 1 or multiple R.sub.8; Alternatively, R.sub.3 and R.sub.3' may be taken together to form a 3-6 membered saturated or partially saturated carbocycle or heterocycle, optionally substituted with 0, 1 or multiple R.sub.8;

[0013] R.sub.4 is chosen from aryl or heteroaryl, each optionally substituted with 0, 1 or multiple R.sub.8;

[0014] R.sub.5 is chosen from alkoxy or benzyloxy, each optionally substituted with 0, 1, or multiple R.sub.8;

[0015] R.sub.6 is chosen from hydrogen, alkoxy, or halo, each optionally substituted with 0, 1, or multiple R.sub.8;

[0016] R.sub.7 is chosen from hydrogen, --C(O)R.sub.9, or --CH.sub.2OC(O)R.sub.9;

[0017] R.sub.8 is chosen from hydrogen, alkyl, aryl, acyl, halo, alkenyl, alkynyl, alkoxy, cyano, or heterocyclyl, each optionally substituted with 0, 1, or multiple R.sub.10;

[0018] R.sub.9 is chosen from alkyl, alkoxy, or aryl, each optionally substituted with 0, 1, or multiple R.sub.8;

[0019] R.sub.10 is chosen from hydrogen, alkyl, aryl, acyl, halo, alkenyl, alkoxy, or heterocyclyl; and

[0020] R.sub.11 is chosen from hydrogen or alkyl, each substituted with 0, 1 or multiple R.sub.8.

[0021] Another embodiment of the present disclosure may include a fungicidal composition for the control or prevention of fungal attack comprising the compounds described above and a phytologically acceptable carrier material.

[0022] Yet another embodiment of the present disclosure may include a method for the control or prevention of fungal attack on a plant, the method including the steps of applying a fungicidally effective amount of one or more of the compounds described above to at least one of the fungus, the plant, and an area adjacent to the plant.

[0023] It will be understood by those skilled in the art that the following terms may include generic "R"-groups within their definitions, e.g., "the term alkoxy refers to an --OR substituent". It is also understood that within the definitions for the following terms, these "R" groups are included for illustration purposes and should not be construed as limiting or being limited by substitutions about Formula I.

[0024] The term "alkyl" refers to a branched, unbranched, or saturated cyclic carbon chain, including, but not limited to, methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tertiary butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like.

[0025] The term "alkenyl" refers to a branched, unbranched or cyclic carbon chain containing one or more double bonds including, but not limited to, ethenyl, propenyl, butenyl, isopropenyl, isobutenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, and the like.

[0026] The terms "aryl" and "Ar" refer to any aromatic ring, mono- or bi-cyclic, containing 0 heteroatoms.

[0027] The term "heterocyclyl" refers to any aromatic or non-aromatic ring, mono- or bi-cyclic, containing one or more heteroatoms

[0028] The term "alkoxy" refers to an --OR substituent.

[0029] The term "acyloxy" refers to an --OC(O)R substituent.

[0030] The term "cyano" refers to a --C.ident.N substituent.

[0031] The term "hydroxyl" refers to a --OH substituent.

[0032] The term "amino" refers to an --N(R).sub.2 substituent.

[0033] The term "arylalkoxy" refers to --O(CH.sub.2).sub.nAr where n is an integer selected from the list 1, 2, 3, 4, 5, or 6.

[0034] The term "haloalkoxy" refers to an --OR--X substituent, wherein X is Cl, F, Br, or I, or any combination thereof.

[0035] The term "haloalkyl" refers to an alkyl, which is substituted with Cl, F, I, or Br or any combination thereof.

[0036] The term "halogen" or "halo" refers to one or more halogen atoms, defined as F, Cl, Br, and I.

[0037] The term "nitro" refers to a --NO.sub.2 substituent.

[0038] The term thioalkyl refers to a --SR substituent.

[0039] Throughout the disclosure, reference to the compounds of Formula I is read as also including all stereoisomers, for example diastereomers, enantiomers, and mixtures thereof. In another embodiment, Formula (I) is read as also including salts or hydrates thereof. Exemplary salts include, but are not limited to: hydrochloride, hydrobromide, hydroiodide, trifluoroacetate, and trifluoromethane sulfonate.

[0040] It is also understood by those skilled in the art that additional substitution is allowable, unless otherwise noted, as long as the rules of chemical bonding and strain energy are satisfied and the product still exhibits fungicidal activity.

[0041] Another embodiment of the present disclosure is a use of a compound of Formula I, for protection of a plant against attack by a phytopathogenic organism or the treatment of a plant infested by a phytopathogenic organism, comprising the application of a compound of Formula I, or a composition comprising the compound to soil, a plant, a part of a plant, foliage, and/or roots.

[0042] Additionally, another embodiment of the present disclosure is a composition useful for protecting a plant against attack by a phytopathogenic organism and/or treatment of a plant infested by a phytopathogenic organism comprising a compound of Formula I and a phytologically acceptable carrier material.

DETAILED DESCRIPTION

[0043] The compounds of the present disclosure may be applied by any of a variety of known techniques, either as the compounds or as formulations comprising the compounds. For example, the compounds may be applied to the roots or foliage of plants for the control of various fungi, without damaging the commercial value of the plants. The materials may be applied in the form of any of the generally used formulation types, for example, as solutions, dusts, wettable powders, flowable concentrate, or emulsifiable concentrates.

[0044] Preferably, the compounds of the present disclosure are applied in the form of a formulation, comprising one or more of the compounds of Formula I with a phytologically acceptable carrier. Concentrated formulations may be dispersed in water, or other liquids, for application, or formulations may be dust-like or granular, which may then be applied without further treatment. The formulations can be prepared according to procedures that are conventional in the agricultural chemical art.

[0045] The present disclosure contemplates all vehicles by which one or more of the compounds may be formulated for delivery and used as a fungicide. Typically, formulations are applied as aqueous suspensions or emulsions. Such suspensions or emulsions may be produced from water-soluble, water-suspendable, or emulsifiable formulations which are solids, usually known as wettable powders; or liquids, usually known as emulsifiable concentrates, aqueous suspensions, or suspension concentrates. As will be readily appreciated, any material to which these compounds may be added may be used, provided it yields the desired utility without significant interference with the activity of these compounds as antifungal agents.

[0046] Wettable powders, which may be compacted to form water-dispersible granules, comprise an intimate mixture of one or more of the compounds of Formula I, an inert carrier and surfactants. The concentration of the compound in the wettable powder may be from about 10 percent to about 90 percent by weight based on the total weight of the wettable powder, more preferably about 25 weight percent to about 75 weight percent. In the preparation of wettable powder formulations, the compounds may be compounded with any finely divided solid, such as prophyllite, talc, chalk, gypsum, Fuller's earth, bentonite, attapulgite, starch, casein, gluten, montmorillonite clays, diatomaceous earths, purified silicates or the like. In such operations, the finely divided carrier and surfactants are typically blended with the compound(s) and milled.

[0047] Emulsifiable concentrates of the compounds of Formula I may comprise a convenient concentration, such as from about 1 weight percent to about 50 weight percent of the compound, in a suitable liquid, based on the total weight of the concentrate. The compounds may be dissolved in an inert carrier, which is either a water-miscible solvent or a mixture of water-immiscible organic solvents, and emulsifiers. The concentrates may be diluted with water and oil to form spray mixtures in the form of oil-in-water emulsions. Useful organic solvents include aromatics, especially the high-boiling naphthalenic and olefinic portions of petroleum such as heavy aromatic naphtha. Other organic solvents may also be used, for example, terpenic solvents, including rosin derivatives, aliphatic ketones, such as cyclohexanone, and complex alcohols, such as 2-ethoxyethanol.

[0048] Emulsifiers which may be advantageously employed herein may be readily determined by those skilled in the art and include various nonionic, anionic, cationic and amphoteric emulsifiers, or a blend of two or more emulsifiers. Examples of nonionic emulsifiers useful in preparing the emulsifiable concentrates include the polyalkylene glycol ethers and condensation products of alkyl and aryl phenols, aliphatic alcohols, aliphatic amines or fatty acids with ethylene oxide, propylene oxides such as the ethoxylated alkyl phenols and carboxylic esters solubilized with the polyol or polyoxyalkylene. Cationic emulsifiers include quaternary ammonium compounds and fatty amine salts. Anionic emulsifiers include the oil-soluble salts (e.g., calcium) of alkylaryl sulphonic acids, oil-soluble salts or sulfated polyglycol ethers and appropriate salts of phosphated polyglycol ether.

[0049] Representative organic liquids which may be employed in preparing the emulsifiable concentrates of the compounds of the present disclosure are the aromatic liquids such as xylene, propyl benzene fractions; or mixed naphthalene fractions, mineral oils, substituted aromatic organic liquids such as dioctyl phthalate; kerosene; dialkyl amides of various fatty acids, particularly the dimethyl amides of fatty glycols and glycol derivatives such as the n-butyl ether, ethyl ether or methyl ether of diethylene glycol, the methyl ether of triethylene glycol, petroleum fractions or hydrocarbons such as mineral oil, aromatic solvents, paraffinic oils, and the like; vegetable oils such as soy bean oil, rape seed oil, olive oil, castor oil, sunflower seed oil, coconut oil, corn oil, cotton seed oil, linseed oil, palm oil, peanut oil, safflower oil, sesame oil, tung oil and the like; esters of the above vegetable oils; and the like. Mixtures of two or more organic liquids may also be employed in the preparation of the emulsifiable concentrate. Organic liquids include xylene, and propyl benzene fractions, with xylene being most preferred in some cases. Surface-active dispersing agents are typically employed in liquid formulations and in an amount of from 0.1 to 20 percent by weight based on the combined weight of the dispersing agent with one or more of the compounds. The formulations can also contain other compatible additives, for example, plant growth regulators and other biologically active compounds used in agriculture.

[0050] Aqueous suspensions comprise suspensions of one or more water-insoluble compounds of Formula I, dispersed in an aqueous vehicle at a concentration in the range from about 1 to about 50 weight percent, based on the total weight of the aqueous suspension. Suspensions are prepared by finely grinding one or more of the compounds, and vigorously mixing the ground material into a vehicle comprised of water and surfactants chosen from the same types discussed above. Other components, such as inorganic salts and synthetic or natural gums, may also be added to increase the density and viscosity of the aqueous vehicle.

[0051] The compounds of Formula I can also be applied as granular formulations, which are particularly useful for applications to the soil. Granular formulations generally contain from about 0.5 to about 10 weight percent, based on the total weight of the granular formulation of the compound(s), dispersed in an inert carrier which consists entirely or in large part of coarsely divided inert material such as attapulgite, bentonite, diatomite, clay or a similar inexpensive substance. Such formulations are usually prepared by dissolving the compounds in a suitable solvent and applying it to a granular carrier which has been preformed to the appropriate particle size, in the range of from about 0.5 to about 3 mm. A suitable solvent is a solvent in which the compound is substantially or completely soluble. Such formulations may also be prepared by making a dough or paste of the carrier and the compound and solvent, and crushing and drying to obtain the desired granular particle.

[0052] Dusts containing the compounds of Formula I may be prepared by intimately mixing one or more of the compounds in powdered form with a suitable dusty agricultural carrier, such as, for example, kaolin clay, ground volcanic rock, and the like. Dusts can suitably contain from about 1 to about 10 weight percent of the compounds, based on the total weight of the dust.

[0053] The formulations may additionally contain adjuvant surfactants to enhance deposition, wetting, and penetration of the compounds onto the target crop and organism. These adjuvant surfactants may optionally be employed as a component of the formulation or as a tank mix. The amount of adjuvant surfactant will typically vary from 0.01 to 1.0 percent by volume, based on a spray-volume of water, preferably 0.05 to 0.5 volume percent. Suitable adjuvant surfactants include, but are not limited to ethoxylated nonyl phenols, ethoxylated synthetic or natural alcohols, salts of the esters or sulphosuccinic acids, ethoxylated organosilicones, ethoxylated fatty amines, blends of surfactants with mineral or vegetable oils, crop oil concentrate (mineral oil (85%)+emulsifiers (15%)); nonylphenol ethoxylate; benzylcocoalkyldimethyl quaternary ammonium salt; blend of petroleum hydrocarbon, alkyl esters, organic acid, and anionic surfactant; C.sub.9-C.sub.11 alkylpolyglycoside; phosphated alcohol ethoxylate; natural primary alcohol (C.sub.12-C.sub.16) ethoxylate; di-sec-butylphenol EO-PO block copolymer; polysiloxane-methyl cap; nonylphenol ethoxylate+urea ammonium nitrate; emulsified methylated seed oil; tridecyl alcohol (synthetic) ethoxylate (8EO); tallow amine ethoxylate (15 EO); PEG(400) dioleate-99. The formulations may also include oil-in-water emulsions such as those disclosed in U.S. patent application Ser. No. 11/495,228, the disclosure of which is expressly incorporated by reference herein.

[0054] The formulations may optionally include combinations that contain other pesticidal compounds. Such additional pesticidal compounds may be fungicides, insecticides, herbicides, nematocides, miticides, arthropodicides, bactericides or combinations thereof that are compatible with the compounds of the present disclosure in the medium selected for application, and not antagonistic to the activity of the present compounds. Accordingly, in such embodiments, the other pesticidal compound is employed as a supplemental toxicant for the same or for a different pesticidal use. The compounds of Formula I and the pesticidal compound in the combination can generally be present in a weight ratio of from 1:100 to 100:1.

[0055] The compounds of the present disclosure may also be combined with other fungicides to form fungicidal mixtures and synergistic mixtures thereof. The fungicidal compounds of the present disclosure are often applied in conjunction with one or more other fungicides to control a wider variety of undesirable diseases. When used in conjunction with other fungicide(s), the presently claimed compounds may be formulated with the other fungicide(s), tank-mixed with the other fungicide(s) or applied sequentially with the other fungicide(s). Such other fungicides may include 2-(thiocyanatomethylthio)-benzothiazole, 2-phenylphenol, 8-hydroxyquinoline sulfate, ametoctradin, amisulbrom, antimycin, Ampelomyces quisqualis, azaconazole, Bacillus subtilis, Bacillus subtilis strain QST713, benalaxyl, benomyl, benthiavalicarb-isopropyl, benzovindiflupyr, benzylaminobenzene-sulfonate (BABS) salt, bicarbonates, biphenyl, bismerthiazol, bitertanol, bixafen, blasticidin-S, borax, Bordeaux mixture, boscalid, bromuconazole, bupirimate, calcium polysulfide, captafol, captan, carbendazim, carboxin, carpropamid, carvone, chlazafenone, chloroneb, chlorothalonil, chlozolinate, Coniothyrium minitans, copper hydroxide, copper octanoate, copper oxychloride, copper sulfate, copper sulfate (tribasic), cuprous oxide, cyazofamid, cyflufenamid, cymoxanil, cyproconazole, cyprodinil, dazomet, debacarb, diammonium ethylenebis-(dithiocarbamate), dichlofluanid, dichlorophen, diclocymet, diclomezine, dichloran, diethofencarb, difenoconazole, difenzoquat ion, diflumetorim, dimethomorph, dimoxystrobin, diniconazole, diniconazole-M, dinobuton, dinocap, diphenylamine, dithianon, dodemorph, dodemorph acetate, dodine, dodine free base, edifenphos, enestrobin, enestroburin, epoxiconazole, ethaboxam, ethoxyquin, etridiazole, famoxadone, fenamidone, fenarimol, fenbuconazole, fenfuram, fenhexamid, fenoxanil, fenpiclonil, fenpropidin, fenpropimorph, fenpyrazamine, fentin, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, fluindapyr, flumorph, fluopicolide, fluopyram, fluoroimide, fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, flutianil, flutolanil, flutriafol, fluxapyroxad, folpet, formaldehyde, fosetyl, fosetyl-aluminium, fuberidazole, furalaxyl, furametpyr, guazatine, guazatine acetates, GY-81, hexachlorobenzene, hexaconazole, hymexazol, imazalil, imazalil sulfate, imibenconazole, iminoctadine, iminoctadine triacetate, iminoctadine tris(albesilate), iodocarb, ipconazole, ipfenpyrazolone, iprobenfos, iprodione, iprovalicarb, isofetamide, isoprothiolane, isopyrazam, isotianil, kasugamycin, kasugamycin hydrochloride hydrate, kresoxium-methyl, laminarin, mancopper, mancozeb, mandipropamid, maneb, mefenoxam, mepanipyrim, mepronil, meptyl-dinocap, mercuric chloride, mercuric oxide, mercurous chloride, metalaxyl, metalaxyl-M, metam, metam-ammonium, metam-potassium, metam-sodium, metconazole, methasulfocarb, methyl iodide, methyl isothiocyanate, metiram, metominostrobin, metrafenone, mildiomycin, myclobutanil, nabam, nitrothal-isopropyl, nuarimol, octhilinone, ofurace, oleic acid (fatty acids), orysastrobin, oxadixyl, oxathiapiprolin, oxine-copper, oxpoconazole fumarate, oxycarboxin, pefurazoate, penconazole, pencycuron, penflufen, pentachlorophenol, pentachlorophenyl laurate, penthiopyrad, phenylmercury acetate, phosphonic acid, phthalide, picoxystrobin, polyoxin B, polyoxins, polyoxorim, potassium bicarbonate, potassium hydroxyquinoline sulfate, probenazole, prochloraz, procymidone, propamocarb, propamocarb hydrochloride, propiconazole, propineb, proquinazid, prothioconazole, pydiflumetofen, pyrametostrobin, pyraoxystrobin, pyraclostrobin, pyraziflumid, pyrazophos, pyribencarb, pyributicarb, pyrifenox, pyrimethanil, pyriofenone, pyroquilon, quinoclamine, quinoxyfen, quintozene, Reynoutria sachalinensis extract, sedaxane, silthiofam, simeconazole, sodium 2-phenylphenoxide, sodium bicarbonate, sodium pentachlorophenoxide, spiroxamine, sulfur, SYP-Z048, tar oils, tebuconazole, tebufloquin, tecnazene, tetraconazole, thiabendazole, thifluzamide, thiophanate-methyl, thiram, tiadinil, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, triazoxide, tricyclazole, tridemorph, trifloxystrobin, triflumizole, triforine, triticonazole, validamycin, valifenalate, valiphenal, vinclozolin, zineb, ziram, zoxamide, Candida oleophila, Fusarium oxysporum, Gliocladium spp., Phlebiopsis gigantea, Streptomyces griseoviridis, Trichoderma spp., (RS)--N-(3,5-dichlorophenyl)-2-(methoxymethyl)-succinimide, 1,2-dichloropropane, 1,3-dichloro-1,1,3,3-tetrafluoroacetone hydrate, 1-chloro-2,4-dinitronaphthalene, 1-chloro-2-nitropropane, 2-(2-heptadecyl-2-imidazolin-1-yl)ethanol, 2,3-dihydro-5-phenyl-1,4-dithi-ine 1,1,4,4-tetraoxide, 2-methoxyethylmercury acetate, 2-methoxyethylmercury chloride, 2-methoxyethylmercury silicate, 3-(4-chlorophenyl)-5-methylrhodanine, 4-(2-nitroprop-1-enyl)phenyl thiocyanateme, ampropylfos, anilazine, azithiram, barium polysulfide, Bayer 32394, benodanil, benquinox, bentaluron, benzamacril; benzamacril-isobutyl, benzamorf, binapacryl, bis(methylmercury) sulfate, bis(tributyltin) oxide, buthiobate, cadmium calcium copper zinc chromate sulfate, carbamorph, CECA, chlobenthiazone, chloraniformethan, chlorfenazole, chlorquinox, climbazole, copper bis(3-phenylsalicylate), copper zinc chromate, coumoxystrobin, cufraneb, cupric hydrazinium sulfate, cuprobam, cyclafuramid, cypendazole, cyprofuram, decafentin, dichlobentiazox, dichlone, dichlozoline, diclobutrazol, dimethirimol, dinocton, dinosulfon, dinoterbon, dipymetitrone, dipyrithione, ditalimfos, dodicin, drazoxolon, EBP, enoxastrobin, ESBP, etaconazole, etem, ethirim, fenaminstrobin, fenaminosulf, fenapanil, fenitropan, fenpicoxamid, flufenoxystrobin, fluotrimazole, furcarbanil, furconazole, furconazole-cis, furmecyclox, furophanate, glyodine, griseofulvin, halacrinate, Hercules 3944, hexylthiofos, ICIA0858, ipfentrifluconazole, isopamphos, isovaledione, mandestrobin, mebenil, mecarbinzid, mefentrifluconazole, metazoxolon, methfuroxam, methylmercury dicyandiamide, metsulfovax, milneb, mucochloric anhydride, myclozolin, N-3,5-dichlorophenyl-succinimide, N-3-nitrophenylitaconimide, natamycin, N-ethylmercurio-4-toluenesulfonanilide, nickel bis(dimethyldithiocarbamate), OCH, phenylmercury dimethyldithiocarbamate, phenylmercury nitrate, phosdiphen, prothiocarb; prothiocarb hydrochloride, pyracarbolid, pyridinitril, pyrisoxazole, pyroxychlor, pyroxyfur, quinacetol; quinacetol sulfate, quinazamid, quinconazole, quinofumelin, rabenzazole, salicylanilide, SSF-109, sultropen, tecoram, thiadifluor, thicyofen, thiochlorfenphim, thiophanate, thioquinox, tioxymid, triamiphos, triarimol, triazbutil, trichlamide, triclopyricarb, triflumezopyrim, urbacid, zarilamid, and any combinations thereof.

[0056] Additionally, the compounds described herein may be combined with other pesticides, including insecticides, nematocides, miticides, arthropodicides, bactericides or combinations thereof that are compatible with the compounds of the present disclosure in the medium selected for application, and not antagonistic to the activity of the present compounds to form pesticidal mixtures and synergistic mixtures thereof. The fungicidal compounds of the present disclosure may be applied in conjunction with one or more other pesticides to control a wider variety of undesirable pests. When used in conjunction with other pesticides, the presently claimed compounds may be formulated with the other pesticide(s), tank-mixed with the other pesticide(s) or applied sequentially with the other pesticide(s). Typical insecticides include, but are not limited to: 1,2-dichloropropane, abamectin, acephate, acetamiprid, acethion, acetoprole, acrinathrin, acrylonitrile, alanycarb, aldicarb, aldoxycarb, aldrin, allethrin, allosamidin, allyxycarb, alpha-cypermethrin, alpha-ecdysone, alpha-endosulfan, amidithion, aminocarb, amiton, amiton oxalate, amitraz, anabasine, athidathion, azadirachtin, azamethiphos, azinphos-ethyl, azinphos-methyl, azothoate, barium hexafluorosilicate, barthrin, bendiocarb, benfuracarb, bensultap, beta-cyfluthrin, beta-cypermethrin, bifenthrin, bioallethrin, bioethanomethrin, biopermethrin, bistrifluron, borax, boric acid, bromfenvinfos, bromocyclen, bromo-DDT, bromophos, bromophos-ethyl, bufencarb, buprofezin, butacarb, butathiofos, butocarboxim, butonate, butoxycarboxim, cadusafos, calcium arsenate, calcium polysulfide, camphechlor, carbanolate, carbaryl, carbofuran, carbon disulfide, carbon tetrachloride, carbophenothion, carbosulfan, cartap, cartap hydrochloride, chlorantraniliprole, chlorbicyclen, chlordane, chlordecone, chlordimeform, chlordimeform hydrochloride, chlorethoxyfos, chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, chloroform, chloropicrin, chlorphoxim, chlorprazophos, chlorpyrifos, chlorpyrifos-methyl, chlorthiophos, chromafenozide, cinerin I, cinerin II, cinerins, cismethrin, cloethocarb, closantel, clothianidin, copper acetoarsenite, copper arsenate, copper naphthenate, copper oleate, coumaphos, coumithoate, crotamiton, crotoxyphos, crufomate, cryolite, cyanofenphos, cyanophos, cyanthoate, cyantraniliprole, cyclethrin, cycloprothrin, cyfluthrin, cyhalothrin, cypermethrin, cyphenothrin, cyromazine, cythioate, DDT, decarbofuran, deltamethrin, demephion, demephion-O, demephion-S, demeton, demeton-methyl, demeton-O, demeton-O-methyl, demeton-S, demeton-S-methyl, demeton-S-methylsulphon, diafenthiuron, dialifos, diatomaceous earth, diazinon, dicapthon, dichlofenthion, dichlorvos, dicresyl, dicrotophos, dicyclanil, dieldrin, diflubenzuron, dilor, dimefluthrin, dimefox, dimetan, dimethoate, dimethrin, dimethylvinphos, dimetilan, dinex, dinex-diclexine, dinoprop, dinosam, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, dioxathion, disulfoton, dithicrofos, d-limonene, DNOC, DNOC-ammonium, DNOC-potassium, DNOC-sodium, doramectin, ecdysterone, emamectin, emamectin benzoate, EMPC, empenthrin, endosulfan, endothion, endrin, EPN, epofenonane, eprinomectin, esdepallethrine, esfenvalerate, etaphos, ethiofencarb, ethion, ethiprole, ethoate-methyl, ethoprophos, ethyl formate, ethyl-DDD, ethylene dibromide, ethylene dichloride, ethylene oxide, etofenprox, etrimfos, EXD, famphur, fenamiphos, fenazaflor, fenchlorphos, fenethacarb, fenfluthrin, fenitrothion, fenobucarb, fenoxacrim, fenoxycarb, fenpirithrin, fenpropathrin, fensulfothion, fenthion, fenthion-ethyl, fenvalerate, fipronil, flonicamid, flubendiamide, flucofuron, flucycloxuron, flucythrinate, flufenerim, flufenoxuron, flufenprox, fluvalinate, fonofos, formetanate, formetanate hydrochloride, formothion, formparanate, formparanate hydrochloride, fosmethilan, fospirate, fosthietan, furathiocarb, furethrin, gamma-cyhalothrin, gamma-HCH, halfenprox, halofenozide, HCH, HEOD, heptachlor, heptenophos, heterophos, hexaflumuron, HHDN, hydramethylnon, hydrogen cyanide, hydroprene, hyquincarb, imidacloprid, imiprothrin, indoxacarb, iodomethane, IPSP, isazofos, isobenzan, isocarbophos, isodrin, isofenphos, isofenphos-methyl, isoprocarb, isoprothiolane, isothioate, isoxathion, ivermectin, jasmolin I, jasmolin II, jodfenphos, juvenile hormone I, juvenile hormone II, juvenile hormone III, kelevan, kinoprene, lambda-cyhalothrin, lead arsenate, lepimectin, leptophos, lindane, lirimfos, lufenuron, lythidathion, malathion, malonoben, mazidox, mecarbam, mecarphon, menazon, mephosfolan, mercurous chloride, mesulfenfos, metaflumizone, methacrifos, methamidophos, methidathion, methiocarb, methocrotophos, methomyl, methoprene, methoxychlor, methoxyfenozide, methyl bromide, methyl isothiocyanate, methylchloroform, methylene chloride, metofluthrin, metolcarb, metoxadiazone, mevinphos, mexacarbate, milbemectin, milbemycin oxime, mipafox, mirex, molosultap, monocrotophos, monomehypo, monosultap, morphothion, moxidectin, naftalofos, naled, naphthalene, nicotine, nifluridide, nitenpyram, nithiazine, nitrilacarb, novaluron, noviflumuron, omethoate, oxamyl, oxydemeton-methyl, oxydeprofos, oxydisulfoton, para-dichlorobenzene, parathion, parathion-methyl, penfluron, pentachlorophenol, permethrin, phenkapton, phenothrin, phenthoate, phorate, phosalone, phosfolan, phosmet, phosnichlor, phosphamidon, phosphine, phoxim, phoxim-methyl, pirimetaphos, pirimicarb, pirimiphos-ethyl, pirimiphos-methyl, potassium arsenite, potassium thiocyanate, pp'-DDT, prallethrin, precocene I, precocene II, precocene III, primidophos, profenofos, profluralin, promacyl, promecarb, propaphos, propetamphos, propoxur, prothidathion, prothiofos, prothoate, protrifenbute, pyraclofos, pyrafluprole, pyrazophos, pyresmethrin, pyrethrin I, pyrethrin II, pyrethrins, pyridaben, pyridalyl, pyridaphenthion, pyrifluquinazon, pyrimidifen, pyrimitate, pyriprole, pyriproxyfen, quassia, quinalphos, quinalphos-methyl, quinothion, rafoxanide, resmethrin, rotenone, ryania, sabadilla, schradan, selamectin, silafluofen, silica gel, sodium arsenite, sodium fluoride, sodium hexafluorosilicate, sodium thiocyanate, sophamide, spinetoram, spinosad, spiromesifen, spirotetramat, sulcofuron, sulcofuron-sodium, sulfluramid, sulfotep, sulfoxaflor, sulfuryl fluoride, sulprofos, tau-fluvalinate, tazimcarb, TDE, tebufenozide, tebufenpyrad, tebupirimfos, teflubenzuron, tefluthrin, temephos, TEPP, terallethrin, terbufos, tetrachloroethane, tetrachlorvinphos, tetramethrin, tetramethylfluthrin, theta-cypermethrin, thiacloprid, thiamethoxam, thicrofos, thiocarboxime, thiocyclam, thiocyclam oxalate, thiodicarb, thiofanox, thiometon, thiosultap, thiosultap-disodium, thiosultap-monosodium, thuringiensin, tolfenpyrad, tralomethrin, transfluthrin, transpermethrin, triarathene, triazamate, triazophos, trichlorfon, trichlormetaphos-3, trichloronat, trifenofos, triflumuron, trimethacarb, triprene, vamidothion, vaniliprole, XMC, xylylcarb, zeta-cypermethrin, zolaprofos, and any combinations thereof.

[0057] Additionally, the compounds described herein may be combined with herbicides that are compatible with the compounds of the present disclosure in the medium selected for application, and not antagonistic to the activity of the present compounds to form pesticidal mixtures and synergistic mixtures thereof. The fungicidal compounds of the present disclosure may be applied in conjunction with one or more herbicides to control a wide variety of undesirable plants. When used in conjunction with herbicides, the presently claimed compounds may be formulated with the herbicide(s), tank-mixed with the herbicide(s) or applied sequentially with the herbicide(s). Typical herbicides include, but are not limited to: 4-CPA; 4-CPB; 4-CPP; 2,4-D; 3,4-DA; 2,4-DB; 3,4-DB; 2,4-DEB; 2,4-DEP; 3,4-DP; 2,3,6-TBA; 2,4,5-T; 2,4,5-TB; acetochlor, acifluorfen, aclonifen, acrolein, alachlor, allidochlor, alloxydim, allyl alcohol, alorac, ametridione, ametryn, amibuzin, amicarbazone, amidosulfuron, aminocyclopyrachlor, aminopyralid, amiprofos-methyl, amitrole, ammonium sulfamate, anilofos, anisuron, asulam, atraton, atrazine, azafenidin, azimsulfuron, aziprotryne, barban, BCPC, beflubutamid, benazolin, bencarbazone, benfluralin, benfuresate, bensulfuron, bensulide, bentazone, benzadox, benzfendizone, benzipram, benzobicyclon, benzofenap, benzofluor, benzoylprop, benzthiazuron, bicyclopyrone, bifenox, bilanafos, bispyribac, borax, bromacil, bromobonil, bromobutide, bromofenoxim, bromoxynil, brompyrazon, butachlor, butafenacil, butamifos, butenachlor, buthidazole, buthiuron, butralin, butroxydim, buturon, butylate, cacodylic acid, cafenstrole, calcium chlorate, calcium cyanamide, cambendichlor, carbasulam, carbetamide, carboxazole chlorprocarb, carfentrazone, CDEA, CEPC, chlomethoxyfen, chloramben, chloranocryl, chlorazifop, chlorazine, chlorbromuron, chlorbufam, chloreturon, chlorfenac, chlorfenprop, chlorflurazole, chlorflurenol, chloridazon, chlorimuron, chlornitrofen, chloropon, chlorotoluron, chloroxuron, chloroxynil, chlorpropham, chlorsulfuron, chlorthal, chlorthiamid, cinidon-ethyl, cinmethylin, cinosulfuron, cisanilide, clethodim, cliodinate, clodinafop, clofop, clomazone, clomeprop, cloprop, cloproxydim, clopyralid, cloransulam, CMA, copper sulfate, CPMF, CPPC, credazine, cresol, cumyluron, cyanatryn, cyanazine, cycloate, cyclosulfamuron, cycloxydim, cycluron, cyhalofop, cyperquat, cyprazine, cyprazole, cypromid, daimuron, dalapon, dazomet, delachlor, desmedipham, desmetryn, di-allate, dicamba, dichlobenil, dichloralurea, dichlormate, dichlorprop, dichlorprop-P, diclofop, diclosulam, diethamquat, diethatyl, difenopenten, difenoxuron, difenzoquat, diflufenican, diflufenzopyr, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimethenamid-P, dimexano, dimidazon, dinitramine, dinofenate, dinoprop, dinosam, dinoseb, dinoterb, diphenamid, dipropetryn, diquat, disul, dithiopyr, diuron, DMPA, DNOC, DSMA, EBEP, eglinazine, endothal, epronaz, EPTC, erbon, esprocarb, ethalfluralin, ethametsulfuron, ethidimuron, ethiolate, ethofumesate, ethoxyfen, ethoxysulfuron, etinofen, etnipromid, etobenzanid, EXD, fenasulam, fenoprop, fenoxaprop, fenoxaprop-P, fenoxasulfone, fenteracol, fenthiaprop, fentrazamide, fenuron, ferrous sulfate, flamprop, flamprop-M, flazasulfuron, florasulam, fluazifop, fluazifop-P, fluazolate, flucarbazone, flucetosulfuron, fluchloralin, flufenacet, flufenican, flufenpyr, flumetsulam, flumezin, flumiclorac, flumioxazin, flumipropyn, fluometuron, fluorodifen, fluoroglycofen, fluoromidine, fluoronitrofen, fluothiuron, flupoxam, flupropacil, flupropanate, flupyrsulfuron, fluridone, flurochloridone, fluroxypyr, flurtamone, fluthiacet, fomesafen, foramsulfuron, fosamine, furyloxyfen, glufosinate, glufosinate-P, glyphosate, halauxifen, halosafen, halosulfuron, haloxydine, haloxyfop, haloxyfop-P, hexachloroacetone, hexaflurate, hexazinone, imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, indanofan, indaziflam, iodobonil, iodomethane, iodosulfuron, ioxynil, ipazine, ipfencarbazone, iprymidam, isocarbamid, isocil, isomethiozin, isonoruron, isopolinate, isopropalin, isoproturon, isouron, isoxaben, isoxachlortole, isoxaflutole, isoxapyrifop, karbutilate, ketospiradox, lactofen, lenacil, linuron, MAA, MAMA, MCPA, MCPA-thioethyl, MCPB, mecoprop, mecoprop-P, medinoterb, mefenacet, mefluidide, mesoprazine, mesosulfuron, mesotrione, metam, metamifop, metamitron, metazachlor, metazosulfuron, metflurazon, methabenzthiazuron, methalpropalin, methazole, methiobencarb, methiozolin, methiuron, methometon, methoprotryne, methyl bromide, methyl isothiocyanate, methyldymron, metobenzuron, metobromuron, metolachlor, metosulam, metoxuron, metribuzin, metsulfuron, molinate, monalide, monisouron, monochloroacetic acid, monolinuron, monuron, morfamquat, MSMA, naproanilide, napropamide, naptalam, neburon, nicosulfuron, nipyraclofen, nitralin, nitrofen, nitrofluorfen, norflurazon, noruron, OCH, orbencarb, ortho-dichlorobenzene, orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, oxapyrazon, oxasulfuron, oxaziclomefone, oxyfluorfen, parafluron, paraquat, pebulate, pelargonic acid, pendimethalin, penoxsulam, pentachlorophenol, pentanochlor, pentoxazone, perfluidone, pethoxamid, phenisopham, phenmedipham, phenmedipham-ethyl, phenobenzuron, phenylmercury acetate, picloram, picolinafen, pinoxaden, piperophos, potassium arsenite, potassium azide, potassium cyanate, pretilachlor, primisulfuron, procyazine, prodiamine, profluazol, profluralin, profoxydim, proglinazine, prometon, prometryn, propachlor, propanil, propaquizafop, propazine, propham, propisochlor, propoxycarbazone, propyrisulfuron, propyzamide, prosulfalin, prosulfocarb, prosulfuron, proxan, prynachlor, pydanon, pyraclonil, pyraflufen, pyrasulfotole, pyrazolynate, pyrazosulfuron, pyrazoxyfen, pyribenzoxim, pyributicarb, pyriclor, pyridafol, pyridate, pyriftalid, pyriminobac, pyrimisulfan, pyrithiobac, pyroxasulfone, pyroxsulam, quinclorac, quinmerac, quinoclamine, quinonamid, quizalofop, quizalofop-P, rhodethanil, rimsulfuron, saflufenacil, S-metolachlor, sebuthylazine, secbumeton, sethoxydim, siduron, simazine, simeton, simetryn, SMA, sodium arsenite, sodium azide, sodium chlorate, sulcotrione, sulfallate, sulfentrazone, sulfometuron, sulfosulfuron, sulfuric acid, sulglycapin, swep, TCA, tebutam, tebuthiuron, tefuryltrione, tembotrione, tepraloxydim, terbacil, terbucarb, terbuchlor, terbumeton, terbuthylazine, terbutryn, tetrafluron, thenylchlor, thiazafluron, thiazopyr, thidiazimin, thidiazuron, thiencarbazone-methyl, thifensulfuron, thiobencarb, tiocarbazil, tioclorim, topramezone, tralkoxydim, triafamone, tri-allate, triasulfuron, triaziflam, tribenuron, tricamba, triclopyr, tridiphane, trietazine, trifloxysulfuron, trifluralin, triflusulfuron, trifop, trifopsime, trihydroxytriazine, trimeturon, tripropindan, tritac, tritosulfuron, vernolate, and xylachlor.

[0058] Another embodiment of the present disclosure is a method for the control or prevention of fungal attack. This method comprises applying to the soil, plant, roots, foliage, or locus of the fungus, or to a locus in which the infestation is to be prevented (for example applying to cereal or grape plants), a fungicidally effective amount of one or more of the compounds of Formula I. The compounds are suitable for treatment of various plants at fungicidal levels, while exhibiting low phytotoxicity. The compounds may be useful both in a protectant and/or an eradicant fashion.

[0059] The compounds have been found to have significant fungicidal effect particularly for agricultural use. Many of the compounds are particularly effective for use with agricultural crops and horticultural plants.

[0060] It will be understood by those skilled in the art that the efficacy of the compound for the foregoing fungi establishes the general utility of the compounds as fungicides.

[0061] The compounds have broad ranges of activity against fungal pathogens. Exemplary pathogens may include, but are not limited to, causing agent of wheat leaf blotch (Zymoseptoria tritici), wheat brown rust (Puccinia triticina), wheat stripe rust (Puccinia striiformis), scab of apple (Venturia inaequalis), powdery mildew of grapevine (Uncinula necator), barley scald (Rhynchosporium secalis), blast of rice (Magnaporthe grisea), rust of soybean (Phakopsora pachyrhizi), glume blotch of wheat (Leptosphaeria nodorum), powdery mildew of wheat (Blumeria graminis f. sp. tritici), powdery mildew of barley (Blumeria graminis f. sp. hordei), powdery mildew of cucurbits (Erysiphe cichoracearum), anthracnose of cucurbits (Glomerella lagenarium), leaf spot of beet (Cercospora beticola), early blight of tomato (Alternaria solani), and spot blotch of barley (Cochliobolus sativus). The exact amount of the active material to be applied is dependent not only on the specific active material being applied, but also on the particular action desired, the fungal species to be controlled, and the stage of growth thereof, as well as the part of the plant or other product to be contacted with the compound. Thus, all the compounds, and formulations containing the same, may not be equally effective at similar concentrations or against the same fungal species.

[0062] The compounds are effective in use with plants in a disease-inhibiting and phytologically acceptable amount. The term "disease-inhibiting and phytologically acceptable amount" refers to an amount of a compound that kills or inhibits the plant disease for which control is desired, but is not significantly toxic to the plant. This amount will generally be from about 0.1 to about 1000 ppm (parts per million), with 1 to 500 ppm being preferred. The exact concentration of compound required varies with the fungal disease to be controlled, the type of formulation employed, the method of application, the particular plant species, climate conditions, and the like. A suitable application rate is typically in the range from about 0.10 to about 4 pounds/acre (about 0.01 to 0.45 grams per square meter, g/m.sup.2).

[0063] Any range or desired value given herein may be extended or altered without losing the effects sought, as is apparent to the skilled person for an understanding of the teachings herein.

[0064] The compounds of Formula I may be made using well-known chemical procedures. Intermediates not specifically mentioned in this disclosure are either commercially available, may be made by routes disclosed in the chemical literature, or may be readily synthesized from commercial starting materials utilizing standard procedures.

General Schemes

[0065] The following schemes illustrate approaches to generating picolinamide compounds of Formula (I). The following descriptions and examples are provided for illustrative purposes and should not be construed as limiting in terms of substituents or substitution patterns.

[0066] Compounds of Formula 1.3 and 1.4 wherein R.sub.4 is as originally defined, can be prepared by the methods shown in Scheme 1, steps a-c. Compounds of Formula 1.1, wherein R.sub.4 is as originally defined, can be prepared by treatment of halogens (X) of Formula 1.0, wherein R.sub.4 is as originally defined, first under standard Grignard conditions, using magnesium metal and an alkali base, such as lithium chloride, in a polar, aprotic solvent such as tetrahydrofuran (THF) or diethyl ether (Et.sub.2O), at a temperature of about 0.degree. C. to about 70.degree. C., to afford the Grignard intermediate. The solution is then treated with a metal catalyst, such as iron (III) acetylacetonate, followed by allyl chloride, in a polar aprotic solvent, such as THF, at a temperature of about 0.degree. C. to about 70.degree. C., to give compounds of Formula 1.1, wherein R.sub.4 is as previously defined, and shown in step a. Generally, the composition of compounds of Formula 1.1 derived from this process is a mixture of allyl and E, Z isomers of the styrene derived products. Compounds of Formula 1.1, wherein R.sub.4 is as previously defined, can be isomerized to compounds of Formula 1.2 by treating with a metal catalyst system, such as bis(dibenzylideneactone)palladium (0), a phosphine coordinating reagent, such as tri-tert-butylphosphine, and an acid chloride, such as isobutyryl chloride, in an aromatic hydrocarbon solvent such as toluene, at a temperature of about 25.degree. C. to 100.degree. C., to afford compounds of Formula 1.2, wherein R.sub.4 is as originally defined, and shown in step b. Alternatively, compounds of Formula 1.2, wherein R.sub.4 is as originally defined, can be isomerized using the conditions of Mayer, M.; Welther, A.; Jacobi von Wangelin, A. ChemCatChem. 2011, 3, 1567-1571, and shown in step b. Epoxides of Formulas 1.3 and 1.4, wherein R.sub.4 is as previously defined, can be obtained by a catalytic asymmetric epoxidation method using oxone as oxidant and a fructose derived ketone as described by Wang, Z-X; Tu, Y.; Frohn, M.; Zhang, J-R.; Shi, Y. J. Am. Chem. Soc. 1997, 119, 11224-11235, and depicted in step c. It will be understood by those skilled in the art that epoxides of Formulae 1.3 and 1.4, wherein R.sub.4 is as previously defined, can be prepared by other catalytic asymmetric epoxidation methods, including, but not limited to, dioxiranes derived from other chiral ketones; catalytic metal salen complexes using an oxidant, such

##STR00004##

as dioxygen or sodium hypochlorite; chiral iminium salts using oxone as the oxidizing species; chiral organic oxaziridine salts; and enzymatic epoxidation biocatalysts, such as monooxygenases and hydrolases. In certain other cases, compounds of Formula 1.2, wherein R.sub.4 is as previously defined, can be prepared by the oxo-metathesis method of Franzen (Eur. J. Org. Chem. 2015, 1834) and shown in step d. Treatment of aldehydes of Formula 1.5, wherein R.sub.4 is as previously defined, with an alkene, such as 2-methyl-2-butene, and a Lewis acidic catalyst, such as trityl tetrafluoroborate, in a polar, aprotic solvent, such as dichloromethane, at a temperature of about -78.degree. C. to about room temperature, affords trans-alkenes of Formula 1.2, wherein R.sub.4 is as previously defined.

[0067] Compounds of Formulas 2.1 and 2.2, wherein R.sub.3, R.sub.3' and R.sub.4 are as previously defined, and R.sub.3 and R.sub.3' may or may not be equivalent, can be prepared by the method shown in Scheme 2, step a. Subjection of epoxides of Formulas 1.3 and 1.4, wherein R.sub.4 is as previously defined, to an

##STR00005##

organometallic nucleophile, such as an alkyl magnesium halide, in the presence of a metal halide, such as copper iodide, in a polar, aprotic solvent, such as THF or Et.sub.2O, at a temperature of about -78.degree. C. to 55.degree. C., affords compounds of Formulas 2.1 and 2.2, wherein R.sub.3, R.sub.3' and R.sub.4 are as previously defined, and R.sub.3 and R.sub.3' may or may not be equivalent, and shown in step a.

[0068] In certain cases, it is beneficial to employ an alkenyl organometallic reagent as the carbon nucleophile and shown in Scheme 3. Compounds of Formulas 3.1 and 3.3, wherein R.sub.3 and R.sub.4 are as previously defined, can be prepared by treating epoxides of Formulas 1.3 and 1.4, wherein R.sub.4 is as previously defined, with an alkenyl magnesium halide, such as prop-1-en-2-ylmagnesium bromide, in the presence of a metal halide, such as copper iodide, in a polar, aprotic solvent, such as THF or Et.sub.2O, at a temperature of about -78.degree. C. to 25.degree. C., and shown in step a. Compounds of

##STR00006##

Formulas 3.2 and 3.4, wherein R.sub.3 and R.sub.4 are as previously defined, can be prepared by treatment of compounds of Formulas 3.1 and 3.3, wherein R.sub.3 and R.sub.4 are as previously defined, with a metal hydrogenation catalyst, such as tris(triphenylphosphine)rhodium(I) chloride (Wilkinson's catalyst) in a polar, aprotic solvent, such as THF, in the presence of a hydrogen atmosphere (1-4 atm); or, alternatively, with palladium absorbed on carbon, in a polar solvent, such as THF, in the presence of a hydrogen atmosphere (1-4 atm), and shown in step b.

[0069] In certain additional examples, compounds of Formula 4.2, wherein R.sub.3, R.sub.3' and R.sub.4 are as previously defined and R.sub.3 and R.sub.3' may or may not be equivalent, can be prepared by the procedure shown in Scheme 4, steps a and b. Compounds of Formula 2.1, wherein R.sub.3, R.sub.3' and R.sub.4 are as previously defined and R.sub.3 and R.sub.3' may or may not be equivalent, can be treated with an oxidizing reagent, such as the Dess-Martin periodinane, in a polar solvent such as dichloromethane (CH.sub.2Cl.sub.2), at a temperature of about 0.degree. C. to 50.degree. C., to give compounds of Formula 4.1, wherein R.sub.3, R.sub.3' and R.sub.4 are as previously defined and R.sub.3 and R.sub.3' may or may not be equivalent, and shown in a. Compounds of Formula 4.1, wherein R.sub.3, R.sub.3' and R.sub.4 are as previously defined and R.sub.3 and R.sub.3' may or may not be equivalent, can be treated with a chiral oxazaborolidine catalyst, such as (R)-1-methyl-3,3-diphenylhexahydropyrrolo[1,2-c][1,3,2]oxazaborole, in the presence of a boron hydride reducing agent, such as borane-dimethyl sulfide complex, in an aprotic solvent, such as toluene or

##STR00007##

THF, at a temperature from about -78.degree. C. to about room temperature, to afford compounds of Formula 4.2, wherein R.sub.3, R.sub.3' and R.sub.4 are as previously defined and R.sub.3 and R.sub.3' may or may not be equivalent, and shown in b. Typical diastereomeric ratios obtained in b are generally in the 2:1 to 5:1 range with the anti isomer being favored over the syn. It will be understood by those skilled in the art that compounds of Formula 4.1, wherein R.sub.3, R.sub.3' and R.sub.4 are as previously defined and R.sub.3 and R.sub.3' may or may not be equivalent, can be enantioselective reduced by other chiral catalyst/hydride reducing agent combinations, including, but not limited to, chirally modified lithium aluminum hydride or sodium borohydride reagents, phosphoramide catalysts, transfer hydrogenation catalyzed by chiral metal complexes, phase transfer catalysts, or enantioselective hydrogenation of pro-chiral ketones by enzymatic catalysis.

[0070] In yet other examples, it is beneficial to prepare compounds of Formula 2.1 and 2.2, wherein R.sub.3, R.sub.3' and R.sub.4 are as previously defined, and R.sub.3 and R.sub.3' may or may not be equivalent, by the method shown in Scheme 4A. Treatment of substituted acetic acids of Formula 4A.0, wherein R.sub.4 is as previously defined, with two equivalents of a strong base, such as isopropylmagnesium chloride, and an alkylating reagent, such as 2-iodopropane, in a polar aprotic solvent, such as THF, at a temperature of about 25.degree. C. to about 70.degree. C. gives compounds of Formula 4A.1, wherein R.sub.3, R.sub.3' and R.sub.4 are as previously defined, and R.sub.3 and R.sub.3' may or may not be equivalent, and shown in step a. Compounds of Formula 4A.1, wherein R.sub.3, R.sub.3' and R.sub.4 are as previously defined and R.sub.3 and R.sub.3' may or may not be equivalent, can be treated with an amine, such as N,O-dimethylhydroxylamine

##STR00008##

hydrochloride, a coupling reagent, such as 3-(ethyliminomethyleneamino)-N,N-dimethylpropan-1-amine hydrochloride (EDC) or a polymer-supported carbodiimide (PS-CDI), and a catalyst, such as N,N-dimethylpyridin-4-amine (DMAP), in a halogenated or polar, aprotic solvent, such as CH.sub.2Cl.sub.2 or THF to afford compounds of Formula 4A.2, wherein R.sub.3, R.sub.3' and R.sub.4 are as originally defined, and R.sub.3 and R.sub.3' may or may not be equivalent, as shown in step b. Treatment of amides of Formula 4A.2, wherein R.sub.3, R.sub.3' and R.sub.4 are as originally defined, and R.sub.3 and R.sub.3' may or may not be equivalent, with a Grignard reagent, such as methylmagnesium bromide, in a polar, aprotic solvent, such as THF, at a temperature of about 0.degree. C. to about 60.degree. C. yields compounds of Formula 4A.3, wherein R.sub.3, R.sub.3' and R.sub.4 are as originally defined, and R.sub.3 and R.sub.3' may or may not be equivalent, and shown in step c. A racemic mixture of compounds of Formula 2.1 and 2.2, wherein R.sub.3, R.sub.3' and R.sub.4 are as previously defined, and R.sub.3 and R.sub.3' may or may not be equivalent, can be prepared by treating compounds of Formula 4A.3, wherein R.sub.3, R.sub.3' and R.sub.4 are as originally defined, and R.sub.3 and R.sub.3' may or may not be equivalent, with a hydride reducing agent, such as lithium aluminum hydride, in a polar, aprotic solvent, such as THF, at a temperature of about -78.degree. C. to about 30.degree. C., to afford and inseparable mixture of compounds of Formula 2.1 and 2.2, wherein R.sub.3, R.sub.3' and R.sub.4 are as previously defined, and R.sub.3 and R.sub.3' may or may not be equivalent, and shown in step d. A racemic mixture of compounds of Formula 2.1 and 2.2, wherein R.sub.3, R.sub.3' and R.sub.4 are as previously defined, and R.sub.3 and R.sub.3' may or may not be equivalent, can be separated by treatment of the mixture with an optically active carboxylic acid, such as (S)-2-methoxy-2-phenylacetic acid, a coupling reagent, such as 3-(ethyliminomethyleneamino)-N,N-dimethylpropan-1-amine hydrochloride (EDC) or a polymer-supported carbodiimide (PS-CDI), and a catalyst, such as N,N-dimethylpyridin-4-amine (DMAP), in a halogenated or polar, aprotic solvent, such as CH.sub.2Cl.sub.2 or THF to afford compounds of Formula 4A.4 and 4A.5, wherein R.sub.3, R.sub.3' and R.sub.4 are as originally defined, and R.sub.3 and R.sub.3' may or may not be equivalent, as shown in step e. The diastereomeric mixture can then separated into its individual components via silica gel chromatography using a mobile phase, such as 10% tert-butyl methyl ether in hexanes, as the eluant. The individual diastereomers, compounds of Formula 4A.4 and 4A.5, wherein R.sub.3, R.sub.3' and R.sub.4 are as originally defined, and R.sub.3 and R.sub.3' may or may not be equivalent, can be treated with a carbonate base, such as potassium carbonate, in a polar, alcoholic solvent, such as methanol, at a temperature of about 25.degree. C. to about 60.degree. C., to give compounds of Formula 2.1 and 2.2, wherein R.sub.3, R.sub.3' and R.sub.4 are as previously defined, and R.sub.3 and R.sub.3' may or may not be equivalent, and shown in step f.

[0071] In certain additional examples, compounds of Formula 5.5 and 5.9, wherein R.sub.3, R.sub.3' and R.sub.4 are as previously defined and R.sub.3 and R.sub.3' may or may not be equivalent, can be prepared by the procedure shown in Scheme 5, steps a-i. The compound of Formula 5.0 can be treated with an aryl or heteroaryl organometallic reagent, such as phenylmagnesium bromide, in a polar aprotic solvent, such as THF or Et.sub.2O, at a temperature of about 0.degree. C. to room temperature, to afford compounds of Formula 5.1, wherein R.sub.4 is as originally defined, and shown in step a. Subjection of compounds of Formula 5.1 to an oxidization procedure, such as the Swern process (oxalyl chloride, DMSO, Et.sub.3N, CH.sub.2Cl.sub.2), affords compounds of Formula 5.2, wherein R.sub.4 is as originally defined, depicted in b. Alternatively, compounds of Formula 5.2, wherein R.sub.4 is as originally defined, can be prepared by treatment of pyrolidine amide 5.15 with an arylmagnesium halide, such as phenylmagnesium bromide, in a polar, aprotic solvent, such as THF, at a temperature of about -20.degree. C. to about 40.degree. C. to give compounds of Formula 5.2, wherein R.sub.4 is as originally defined, and shown in step b2. Compounds of Formula 5.3, wherein R.sub.3, R.sub.3' and R.sub.4 are as previously defined, and

##STR00009##

R.sub.3 and R.sub.3' may or may not be equivalent, can be obtained by treating compounds of Formula 5.2, wherein R.sub.4 is as originally defined, with an organometallic nucleophile, such as isopropylmagnesium bromide, in a polar aprotic solvent, such as THF or Et.sub.2O, at a temperature of about 0.degree. C. to room temperature, as depicted in step c. Compounds of Formula 5.4, wherein R.sub.3, R.sub.3', and R.sub.4 are as previously defined and R.sub.3 and R.sub.3' may or may not be equivalent, and R.sub.4 is not an electron-deficient aryl or heteroaryl group, can be obtained by treating the compounds of Formula 5.3, wherein R.sub.3, R.sub.3' are as previously defined and may or may not be equivalent, and R.sub.4 is not an electron-deficient aryl or heteroaryl group, with a mixture of a hydride reagent, such as triethylsilane (Et.sub.3SiH), and an acid, such as 2,2,2-trifluoroacetic acid (TFA) in a halogenated solvent such as dichloromethane (DCM) at a temperature of about 0.degree. C. to 23.degree. C., as depicted in d. Compounds of Formula 5.5, wherein R.sub.3, R.sub.3', and R.sub.4 are as originally defined and R.sub.3 may or may not be equivalent to R.sub.3', can be prepared from compounds of Formula 5.4, wherein R.sub.3, R.sub.3', and R.sub.4 are as originally defined and R.sub.3 may or may not be equivalent to R.sub.3', by treating with a metal catalyst such as palladium on carbon (Pd/C) in a polar protic solvent, such as ethanol (EtOH), in a hydrogen atmosphere (1-4 atm) at a temperature of about 25.degree. C. to 65.degree. C., or with an alternate source of hydrogen, such as cyclohexene, in a polar solvent such as EtOH, and shown in step e. In certain other cases, it is beneficial to synthesize compounds of Formula 5.9, wherein R.sub.3 and R.sub.4 are as originally defined, by the method shown in steps f-i. Compounds of Formula 5.2, wherein R.sub.4 is as previously defined, can be treated with an alkenyl organometallic reagent, such as isopropenylmagnesium bromide, in a polar aprotic solvent, such as THF or Et.sub.2O, at a temperature of about 0.degree. C. to room temperature, to afford compounds of Formula 5.6, wherein R.sub.3 and R.sub.4 are as originally defined, and shown in step f. Compounds of Formula 5.7, wherein R.sub.3 and R.sub.4 are as previously defined, can be prepared by treatment of compounds of Formula 5.6, wherein R.sub.3 and R.sub.4 are as previously defined, with a metal hydrogenation catalyst, such as tris(triphenylphosphine)rhodium(I) chloride (Wilkinson's catalyst) in a polar, aprotic solvent, such as THF, in the presence of a hydrogen atmosphere (1-4 atm), and shown in g. Compounds of Formula 5.8, wherein R.sub.3 and R.sub.4 are as previously defined, and R.sub.4 is not an electron-deficient aryl or heteroaryl group, can be obtained by treating the compounds of Formula 5.7, wherein R.sub.3 and R.sub.4 are as previously defined, and R.sub.4 is not an electron-deficient aryl or heteroaryl group, with a mixture of a hydride reagent, such as triethylsilane (Et.sub.3SiH), and an acid, such as 2,2,2-trifluoroacetic acid (TFA) in a halogenated solvent such as dichloromethane (DCM) at a temperature of about 0.degree. C. to 23.degree. C., as depicted in h. Compounds of Formula 5.9, wherein R.sub.3 and R.sub.4 are as previously defined, can be prepared by treatment of compounds of Formula 5.8, wherein R.sub.3 and R.sub.4 are as previously defined, with a metal hydrogenation catalyst, such as tris(triphenylphosphine)rhodium(I) chloride (Wilkinson's catalyst) in a polar, aprotic solvent, such as THF, in the presence of a hydrogen atmosphere (1-4 atm); or, alternatively, with palladium absorbed on carbon, in a polar solvent, such as THF, in the presence of a hydrogen atmosphere (1-4 atm), and shown in step i.

[0072] In certain other examples, compounds of Formula 5.5, wherein R.sub.3, R.sub.3', and R.sub.4, are as originally defined, and R.sub.3 and R.sub.3' may or may not be equivalent, may also be prepared according to the method outlined in Scheme 6, steps a and b. Treatment of compounds of Formula 2.1, wherein R.sub.3, R.sub.3', and R.sub.4 are as originally defined, and R.sub.3 and R.sub.3' may or may not be equivalent, with an

##STR00010##

electron deficient benzoic acid, such as p-nitrobenzoic acid, a phosphine nucleophile, such as triphenylphosphine; and a diazene coupling reagent, such as diethyl (E)-diazene-1,2-dicarboxylate, in a polar, aprotic solvent, such as THF, at a temperature of about 0.degree. C. to about 25.degree. C. affords compounds of Formula 6.1, wherein R.sub.3, R.sub.3', and R.sub.4 are as originally defined, and R.sub.3 and R.sub.3' may or may not be equivalent, as depicted in step a. In step b, compounds of Formula 6.1, wherein R.sub.3, R.sub.3', and R.sub.4 are as originally defined, and R.sub.3 and R.sub.3' may or may not be equivalent, can be treated with an aqueous solution of an inorganic base, such as sodium hydroxide, in a polar aprotic solvent, such as THF, at a temperature of about 0.degree. C. to about 40.degree. C. to afford compounds of Formula 5.5, wherein R.sub.3, R.sub.3', and R.sub.4 are as originally defined, and R.sub.3 and R.sub.3' may or may not be equivalent.

[0073] Compounds of Formula 7.2, wherein R.sub.1, R.sub.3, R.sub.3', R.sub.4, and R.sub.11, are as originally defined, and R.sub.3 and R.sub.3' may or may not be equivalent, may be prepared according to the method outlined in Scheme 7, step a. Alcohols of Formula 5.5, wherein R.sub.3, R.sub.3', and R.sub.4, are as originally defined, and R.sub.3 and R.sub.3' may or may not be equivalent, can be treated with compounds of Formula 7.1, wherein R.sub.1 and R.sub.11 are as originally defined, a coupling reagent, such as 3-(ethyliminomethyleneamino)-N,N-dimethylpropan-1-amine hydrochloride (EDC) or a polymer-supported carbodiimide (PS-CDI), and a catalyst, such as N,N-dimethylpyridin-4-amine (DMAP), in a halogenated or polar, aprotic solvent, such as CH.sub.2Cl.sub.2 or THF to afford compounds of Formula 7.2, wherein R.sub.1, R.sub.3, R.sub.3', R.sub.4, and R.sub.11, are as originally defined, and R.sub.3 and R.sub.3' may or may not be equivalent, as shown in step a.

##STR00011##

[0074] Compounds of Formula 7.2, wherein R.sub.1, R.sub.3, R.sub.3', R.sub.4, and R.sub.11, are as originally defined, and R.sub.3 and R.sub.3' may or may not be equivalent, may also be prepared according to the method outlined in Scheme 8, step a. Alcohols of Formula 2.1, wherein R.sub.3, R.sub.3', and R.sub.4, are as originally

##STR00012##

defined, and R.sub.3 and R.sub.3' may or may not be equivalent, can be treated with compounds of Formula 7.1, wherein R.sub.1 and R.sub.11 are as originally defined, a phosphine reagent, such as triphenylphosphine, and a diazine dicarboxylate electrophile, such as diisopropyl (E)-diazene-1,2-dicarboxylate (DIAD), in a polar aprotic solvent, such as THF, at a temperature of about 0.degree. C. to 25.degree. C. to afford compounds of Formula 7.2, wherein R.sub.1, R.sub.3, R.sub.3', R.sub.4, and R.sub.11, are as originally defined, and R.sub.3 and R.sub.3' may or may not be equivalent, as shown in step a.

[0075] Compounds of Formula 9.5, wherein R.sub.1, R.sub.2, R.sub.3, R.sub.3', R.sub.4, R.sub.6, and R.sub.11, are as originally defined, and R.sub.3 and R.sub.3' may or may not be equivalent, can be prepared according to the methods outlined in Scheme 9, steps a-d. Compounds of Formula 9.1, wherein R.sub.1, R.sub.2, R.sub.3, R.sub.3', R.sub.4, and R.sub.11, are as originally defined, and R.sub.3 and R.sub.3' may or may not be equivalent, but not alkenyl, can be treated with an acid, such as a 4 N solution of HCl in dioxane, in a halogenated solvent such as CH.sub.2Cl.sub.2 to afford compounds of Formula 9.2, wherein R.sub.1, R.sub.2, R.sub.3, R.sub.3', R.sub.4, and R.sub.11, are as originally defined, and R.sub.3 and R.sub.3' may or may not be equivalent, but not alkenyl, as shown in step a. Compounds of Formula 9.3, wherein R.sub.1, R.sub.2, R.sub.3, R.sub.3', R.sub.4, and R.sub.11, are as originally defined, and R.sub.3 and R.sub.3' may or may not be equivalent, can be prepared by treating compounds of Formula 9.1, wherein R.sub.1, R.sub.2, R.sub.3, R.sub.3', R.sub.4, and R.sub.11, are as originally defined, and R.sub.3 and R.sub.3' may or may not be equivalent, with an acid, such as 2,2,2-trifluoroacetic acid, in a halogenated solvent such as CH.sub.2Cl.sub.2, as shown in step c. Compounds of Formulas 9.2 and 9.3, wherein R.sub.1, R.sub.2, R.sub.3, R.sub.3', R.sub.4, and R.sub.11, are as originally defined, and R.sub.3 and R.sub.3' may or may not be equivalent, can be treated with compounds of Formula 9.4, wherein R.sub.6 is as originally defined, in the presence of a base, such as diisopropylethylamine, and a peptide coupling reagent, such as benzotriazol-1-yl-oxytripyrrolidinophosphonium hexafluorophosphate (PyBOP) or O-(7-azabenzo-triazol-1-yl)-N,N,N',N'tetramethyluronium hexafluorophosphate (HATU), in an halogenated solvent such as CH.sub.2Cl.sub.2, to afford compounds of Formula 9.5, wherein R.sub.1, R.sub.2, R.sub.3, R.sub.3', R.sub.4, R.sub.6 and R.sub.11, are as originally defined, and R.sub.3 and R.sub.3' may or may not be equivalent, as shown in steps b and d.

##STR00013##

[0076] Compounds of Formula 10.1, wherein R.sub.1, R.sub.2, R.sub.3, R.sub.3', R.sub.4, R.sub.6, R.sub.7, and R.sub.11, are as originally defined, and R.sub.3 and R.sub.3' may or may not be equivalent, can be prepared according to the method outlined in Scheme 10, steps a or b. Compounds of Formula 9.5, wherein R.sub.1, R.sub.2, R.sub.3, R.sub.3', R.sub.4, R.sub.6 and R.sub.11, are as originally defined, and R.sub.3 and R.sub.3' may or may not be equivalent, can be treated with an appropriate alkyl halide with or without a reagent such as sodium iodide (NaI) and an alkali carbonate base, such as sodium (Na.sub.2CO.sub.3) or potassium carbonate (K.sub.2CO.sub.3), in a solvent such as acetone, as shown in step a. Or, alternatively, by treatment with an acyl halide or anhydride in the presence of an amine base, such as pyridine, NEt.sub.3, DMAP, or mixtures thereof, in an aprotic solvent, such as CH.sub.2Cl.sub.2, to afford compounds of Formula 10.1, wherein R.sub.1, R.sub.2, R.sub.3, R.sub.3', R.sub.4, R.sub.6, R.sub.7, and R.sub.11, are as originally defined, and R.sub.3 and R.sub.3' may or may not be equivalent, as shown in step b.

##STR00014##

[0077] Compounds of Formula 11.1 and 11.2, wherein R.sub.1, R.sub.2, R.sub.3, R.sub.3', R.sub.4, R.sub.6, R.sub.7, and R.sub.11, are as originally defined, and R.sub.3 and R.sub.3' may or may not be equivalent, can be prepared according to the method outlined in Scheme 11, steps a and b. Compounds of Formula 9.5, wherein R.sub.1, R.sub.2, R.sub.3, R.sub.3', R.sub.4, R.sub.6, and R.sub.11, are as originally defined, and R.sub.3 and R.sub.3' may or may not be equivalent, can be treated with a thionating reagent such as phosphorus pentasulfide, an additive, such as hexamethyldisiloxane, optionally in a polar aprotic solvent such as acetonitrile (CH.sub.3CN), at a temperature of about 0.degree. C. to 80.degree. C. to afford compounds of Formula 11.1, wherein R.sub.1, R.sub.2, R.sub.3, R.sub.3', R.sub.4, R.sub.6, and R.sub.11, are as originally defined, and R.sub.3 and R.sub.3' may or may not be equivalent, and shown in step a. It will be understood by those skilled in the art that compounds such as Formula 11.1 may also be prepared using other thionating agents including, but not limited to: sulfur, sulfhydric acid, sodium sulfide, sodium hydrosulfide, boron trisulfide, bis(diethylaluminum)sulfide, ammonium sulfide, Lawesson's reagent, ammonium O,O'-diethyl dithiophosphate, rhodanine, or a polymer supported thionating reagent. Additives can include, but not limited to, aluminum oxide (Al.sub.2O.sub.3); inorganic bases, such as potassium carbonate and sodium bicarbonate; organic bases, such as triethylamine, diethylaniline, pyridine and morpholine. Optional solvents can include, but not limited to, aliphatic, alicyclic or aromatic hydrocarbons, such as hexane, cyclohexane or toluene; halogenated hydrocarbons, such as dichloromethane, 1,2-dichloroethane and chlorobenzene; ethers, such as diethyl ether, 1,4-dioxane, THF and 1,2-dimethoxyethane; and other polar aprotic solvents such as pyridine and hexamethylphosphoramide (HMPA). In step b, treatment of compounds of Formula 11.1, wherein R.sub.1, R.sub.2, R.sub.3, R.sub.3', R.sub.4, R.sub.6, and R.sub.11, are as originally defined, and R.sub.3 and R.sub.3' may or may not be equivalent, with an appropriate alkyl halide with or without a reagent such as sodium iodide (NaI) and an alkali carbonate base, such as sodium carbonate (Na.sub.2CO.sub.3) or potassium carbonate (K.sub.2CO.sub.3), in a solvent like acetone at a temperature of about 55.degree. C., or by treatment with an acyl halide or anhydride in the presence of an amine base, such as pyridine, triethylamine (Et.sub.3N), DMAP, or mixtures thereof, in an optional aprotic solvent such as DCM, at a temperature of about 23.degree. C., can afford compounds of Formula 11.2 wherein R.sub.1, R.sub.2, R.sub.3, R.sub.3', R.sub.4, R.sub.6, R.sub.7, and R.sub.11, are as originally defined, and R.sub.3 and R.sub.3' may or may not be equivalent.

##STR00015##

[0078] Compounds of Formula 12.1, wherein R.sub.1, R.sub.2, R.sub.3, R.sub.3', R.sub.4, R.sub.6, and R.sub.11, are as originally defined, and R.sub.3 and R.sub.3' may or may not be equivalent, can be prepared according to the method outlined in Scheme 12, step a. Compounds of Formula 9.5, wherein R.sub.1, R.sub.2, R.sub.3, R.sub.3', R.sub.4, R.sub.6, and R.sub.11, are as originally defined, and R.sub.3 and R.sub.3' may or may not be equivalent, can be treated with a oxidizing reagent such as m-chloroperbenzoic acid (mCPBA) in a polar solvent such as dichloromethane (CH.sub.2Cl.sub.2), at a temperature of about 0.degree. C. to 50.degree. C., to give compounds of Formula 12.1, as shown in a. It will be understood by those skilled in the art that compounds of Formula 12.1, wherein R.sub.1, R.sub.2, R.sub.3, R.sub.3', R.sub.4, R.sub.6, and R.sub.11, are as originally defined, and R.sub.3 and R.sub.3' may or may not be equivalent, may also be prepared using other oxidizing agents, including, bit not limited to:

##STR00016##

hydrogen peroxide, hydrogen peroxide-urea complex, magnesium monoperoxyphthalate hexahydrate (MMPP), peroxyacetic acid, oxone, sodium perchlorate or dimethyl dioxirane.

[0079] Compounds of Formula 13.1 wherein R.sub.1, R.sub.2, R.sub.3, R.sub.3', R.sub.4, R.sub.6, and R.sub.11, are as originally defined, and R.sub.3 and R.sub.3' may or may not be equivalent, can be prepared according to the method outlined in Scheme 13, step a. Compounds of Formula 9.5, wherein R.sub.1, R.sub.2, R.sub.3, R.sub.3', R.sub.4, R.sub.6, and R.sub.11, are as originally defined, and R.sub.3 and R.sub.3' may or may not be equivalent, can be treated with a deactivated carbonyl reagent such as triphosgene, with a base, such as pyridine, in a polar solvent, such as dichloromethane (CH.sub.2Cl.sub.2), at a temperature of about 0.degree. C. to 50.degree. C. to afford compounds of Formula 13.1, wherein R.sub.1, R.sub.2, R.sub.3, R.sub.3', R.sub.4, R.sub.6, and R.sub.11, are as originally defined, and R.sub.3 and R.sub.3' may or may not be equivalent, as depicted in a.

##STR00017##

EXAMPLES

Example 1A: Preparation of (E)-1-methyl-4-(prop-1-en-1-yl)benzene

##STR00018##

[0081] This compound was prepared by the method of Mayer, M.; Welther, A.; Jacobi von Wangelin, A. ChemCatChem. 2011, 3, 1567-1571.

Example 1B: Preparation of (E)-1-fluoro-4-(prop-1-en-1-yl)benzene

##STR00019##

[0083] To a solution of 1-allyl-4-fluorobenzene (1.35 mL, 10 mmol) in toluene (20 mL) was added bis(dibenzylideneacetone)palladium (0.115 g, 0.200 mmol), tri-tert-butylphosphine (10% in hexane) (0.618 ml, 0.200 mmol) and isobutyryl chloride (0.021 ml, 0.200 mmol) in toluene (20.00 ml). The reaction was stirred at 80.degree. C. overnight. The reaction mixture was purified by Isco chromatography (0 to 5% Et.sub.2O in pet ether) to provide the desired product as solution in toluene (20 mL) (1.36 g, 95%). .sup.1H NMR (300 MHz, CDCl.sub.3) .delta. 7.32-7.10 (m, 6H), 2.35 (s, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -115.97.

Example 1C: Preparation of (E)-4-fluoro-2-methoxy-1-(prop-1-en-1-yl)benzene

Step 1: Preparation of (E,Z)-4-fluoro-2-methoxy-1-(prop-1-en-1-yl)benzene

##STR00020##

[0085] To a mixture of magnesium (0.79 g, 32.5 mmol) and lithium chloride (1.52 g, 35.80 mmol) in THF (33 ml) at room temperature was added 1-bromo-4-fluoro-2-methoxybenzene (3.13 mL, 24.39 mmol) and the reaction was stirred at 70.degree. C. for 1.5 hr. The reaction was then cooled to 0.degree. C., and Fe(acac).sub.3 (0.574 g, 1.63 mmol) was added. After 1 minute, allyl chloride (1.33 mL, 16.26 mmol) was added and the reaction was stirred at 0.degree. C. for 30 min. The mixture was warmed to room temperature over 1 hr and was heated at 70.degree. C. overnight. The reaction was cooled and diluted with petroleum ether (100 mL). The reaction was then quenched by the addition of a saturated NH.sub.4Cl solution (100 mL). The mixture was filtered through a Celite.RTM. pad and the layers were separated. The aqueous layer was extracted with petroleum ether (2.times.100 mL) and the combined organic phases were dried over Na.sub.2SO.sub.4 and carefully concentrated (25.degree. C., 250 mbar). The residue was purified by Isco chromatography (100% pet ether as the eluent) to provide (E,Z)-4-fluoro-2-methoxy-1-(prop-1-en-1-yl)benzene (2.25 g, 83% yield) as a colorless oil. This mixture was approximately a 3:1 mixture of E and Z isomers with a trace of the allyl isomer present. This material was used directly in the next step. .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.31 (dd, J=8.3, 6.8 Hz, 1H), 6.65-6.53 (m, 3H), 6.14 (dq, J=15.8, 6.6 Hz, 1H), 3.82 (s, 3H), 1.88 (dd, J=6.6, 1.7 Hz, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -113.30.

Step 2: Preparation of (E)-4-fluoro-2-methoxy-1-(prop-1-en-1-yl)benzene

##STR00021##

[0087] To a solution of (E,Z)-4-fluoro-2-methoxy-1-(prop-1-en-1-yl)benzene (2.25 g, 13.54 mmol) in toluene (27 mL) was added bis(dibenzylideneacetone)palladium (0.156 g, 0.271 mmol), tri-tert-butylphosphine (10% in hexane) (0.84 mL, 0.271 mmol) and isobutyryl chloride (0.028 mL, 0.271 mmol). The reaction was stirred at 80.degree. C. overnight. The reaction mixture was purified by Isco chromatography (100% petroleum ether) to provide the title compound as a 20:1 mixture of E vs Z isomers (2.25 g, 100%). .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.31 (dd, J=8.3, 6.8 Hz, 1H), 6.65-6.53 (m, 3H), 6.14 (dq, J=15.8, 6.6 Hz, 1H), 3.82 (s, 3H), 1.88 (dd, J=6.6, 1.7 Hz, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -113.30.

Example 1D: Preparation of (E)-2,4-dimethyl-1-(prop-1-en-1-yl)benzene

Step 1: Preparation of 1-allyl-2,4-dimethylbenzene

##STR00022##

[0089] To a solution of magnesium (1.17 g, 48.0 mmol) and lithium chloride (2.20 g, 60.0 mmol) in THF (40 ml) at room temperature was added 1-bromo-2,4-dimethylbenzene (5.4 mL, 40.0 mmol) and the reaction was heated gently to reflux with a heat gun. The reaction was cooled to room temperature over 1 hr. The reaction was then cooled to 0.degree. C., and Fe(acac).sub.3 (0.71 g, 2.00 mmol) dissolved in 5 mL of THF was added. After 5 minutes, allyl chloride (4.23 mL, 52.0 mmol) was added and the reaction was stirred at 0.degree. C. for 30 min. The mixture was warmed to room temperature over 1 hr and was heated at 70.degree. C. overnight. The reaction was cooled to 0.degree. C. and quenched by the addition of a saturated NaHCO.sub.3 solution (50 mL). The mixture was extracted with hexane (3.times.40 mL), the combined organic phases were washed with brine (50 mL), dried over Na.sub.2SO.sub.4 and carefully concentrated (25.degree. C., 250 mbar). The residue was purified by Isco chromatography (100% hexane as the eluent) to provide 1-allyl-2,4-dimethylbenzene (2.75 g, 15.04 mmol, 38% yield) as a colorless oil. .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.11-6.87 (m, 3H), 5.93 (ddt, J=16.6, 10.1, 6.4 Hz, 1H), 5.19-4.85 (m, 2H), 3.33 (dd, J=6.4, 1.5 Hz, 2H), 2.29 (s, 3H), 2.25 (s, 3H).

Step 2: Preparation of (E)-2,4-dimethyl-1-(prop-1-en-1-yl)benzene

##STR00023##

[0091] To a 250 mL round bottom flask charged with 1-allyl-2,4-dimethylbenzene (2.75 g, 18.81 mmol) and tris(((Z)-4-oxopent-2-en-2-yl)oxy)iron (0.332 g, 0.940 mmol) in THF (38 mL) was added phenylmagnesium bromide (1.0 M in THF) (9.40 mL, 9.40 mmol) at room temperature. After stirring overnight, the reaction mixture was cooled to 0.degree. C. and quenched by the addition of a saturated solution of NaHCO.sub.3 (50 mL). The combined organic layers were extracted with hexane (3.times.40 mL), washed with brine (50 mL) and dried over Na.sub.2SO.sub.4. Upon concentration in vacuo, the crude residue was purified via automated silica gel chromatography (100% hexanes as the eluent) to afford (E)-2,4-dimethyl-1-(prop-1-en-1-yl)benzene (2.71 g, 16.68 mmol, 89% yield) as a colorless oil. .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.30 (d, J=7.8 Hz, 1H), 7.05-6.86 (m, 2H), 6.56 (dd, J=15.6, 1.9 Hz, 1H), 6.06 (dq, J=15.6, 6.6 Hz, 1H), 2.30 (s, 3H), 2.29 (s, 3H), 1.89 (dd, J=6.6, 1.7 Hz, 3H).

Example 1E: Preparation of (E)-1-methyl-2-(prop-1-en-1-yl)benzene

##STR00024##

[0093] This compound was prepared by the method of Franzen (Eur. J. Org. Chem. 2015, 1834). To a solution of 2-methylbenzaldehyde (48.4 mL, 416 mmol) dissolved in CH.sub.2Cl.sub.2 (300 mL) was added 2-methylbut-2-ene (8.82 mL, 83 mmol) and triphenylmethylium tetrafluoroborate (5.50 g, 16.65 mmol). The reaction was stirred at room temperature for 20 hr. The reaction was quenched by the addition of saturated NaHCO.sub.3 and diluted with excess CH.sub.2Cl.sub.2. The organic layer was separated, dried over MgSO.sub.4, filtered and concentrated at low temperature and mild pressure. The resulting residue was purified by flash chromatography (ISCO, 330 g SiO.sub.2 column, 100% pet ether as the eluent) to give (E)-1-methyl-2-(prop-1-en-1-yl)benzene (10 g, 71.9 mmol, 86% yield) as a clear liquid. .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.39 (d, J=7.0 Hz, 1H), 7.12 (qd, J=5.9, 2.1 Hz, 3H), 6.59 (dd, J=15.6, 1.9 Hz, 1H), 6.10 (dq, J=15.7, 6.6 Hz, 1H), 2.32 (s, 3H), 1.90 (dd, J=6.6, 1.8 Hz, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 137.08, 134.77, 130.11, 128.92, 126.93, 126.70, 125.99, 125.44. EIMS m/z 132.

Example 2A: 2A Denotes that this Epoxide is Commercially Available

Example 2B: Preparation of (2S,3S)-2-methyl-3-(p-tolyl)oxirane

##STR00025##

[0095] To a 500 mL round-bottom flask containing 75 mL of a buffer solution containing 0.05 M Na.sub.2B.sub.4O.sub.7-10H.sub.2O in 4.times.10.sup.-4 M aqueous Na.sub.2(EDTA), was added acetonitrile (117 ml), (E)-1-methyl-4-(prop-1-en-1-yl)benzene (1.24 g, 7.69 mmol), tetrabutylammonium hydrogen sulfate (0.104 g, 0.308 mmol), and (3aS,4'R,7aS)-2,2,2',2'-tetramethyldihydrospiro[[1,3]dioxolo-[4,5-c]pyran- -6,4'-[1,3]dioxolan]-7(7aH)-one (0.596 g, 2.307 mmol). The reaction mixture was cooled to 0.degree. C. with an ice bath. A solution of oxone (6.53 g, 10.61 mmol) in aqueous Na.sub.2(EDTA) (4.times.10.sup.-4 M, 50 mL) and a solution of potassium carbonate (6.17 g, 44.6 mmol) in water (50 mL) were added dropwise through two syringe pumps over a period of 1.5 h (under these conditions, the reaction pH is around 10.5; it is recommended that both oxone and K.sub.2CO.sub.3 be added uniformly over 1.5 h). At this point, the reaction was immediately quenched by the addition of 100 mL each of petroleum ether and water. The layers were separated and the aqueous layer was extracted with petroleum ether (3.times.150 mL). The combined organic layers were washed with brine (150 mL), dried over Na.sub.2SO.sub.4 and concentrated under reduced pressure. The residue was purified by flash chromatography (0 to 10% acetone in hexanes as the eluent) to provide (2S,3S)-2-methyl-3-(p-tolyl)oxirane (1.09 g, 6.99 mmol, 91%) as a colorless oil. .sup.1H NMR (300 MHz, CDCl.sub.3) .delta. 7.15 (s, 4H), 3.54 (d, J=2.1 Hz, 1H), 3.03 (qd, J=5.1, 2.1 Hz, 1H), 2.34 (s, 3H), 1.44 (d, J=5.1 Hz, 3H). EIMS m/z 148.

Example 3A: Preparation of (1S,2R)-1-cyclobutyl-1-(4-fluoro-2-methylphenyl)propan-2-ol

##STR00026##

[0097] A suspension of magnesium (110 mg, 4.51 mmol) was prepared in THF (3 mL) and cooled to 0.degree. C. After 5 min, bromocyclobutane (397 .mu.L, 4.21 mmol) was added in one portion, and the resulting solution was vigorously stirred for 2 hr, slowly warming to room temperature. After 2 hr, the reaction was heated to 55.degree. C. and stirred overnight. In a separate vial, a suspension of copper(I) iodide (401 mg, 2.106 mmol) in diethyl ether (7.5 mL) was cooled to -30.degree. C. in a dry ice/acetonitrile bath. After -5 min, the grignard solution was added via syringe over 30 seconds, and the resulting solution was stirred at -30.degree. C. for 30 min, yielding a turbid dark grey/brown mixture. After 30 min, the reaction was cooled to -78.degree. C. in a dry ice/acetone bath, and (2R,3R)-2-(4-fluoro-2-methylphenyl)-3-methyloxirane (250 mg, 1.504 mmol) was added dropwise via syringe as a solution in diethyl ether (1.5 mL with 2.times.0.5 mL washes). The reaction was then stirred overnight, slowly warming to room temperature. TLC indicated consumption of starting material. The reaction was quenched with sat. aq. NH.sub.4Cl (20 mL) and extracted with diethyl ether (3.times.20 mL). The combined organic layers were dried over Na.sub.2SO.sub.4, filtered and concentrated to afford an oil. The oil was purified via silica gel Isco column chromatography (40 g silica gel column, 35 mL/min, 100% hexanes to 20% acetone:hexanes) to afford (1S,2R)-1-cyclobutyl-1-(4-fluoro-2-methylphenyl)propan-2-ol (133.4 mg, 0.600 mmol, 40% yield) as a clear, colorless oil. .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.14 (dd, J=8.2, 6.1 Hz, 1H), 6.86 (t, J=8.5 Hz, 2H), 3.89 (p, J=6.4 Hz, 1H), 2.84 (dd, J=10.4, 6.0 Hz, 1H), 2.77-2.64 (m, 1H), 2.35 (s, 3H), 2.24-2.12 (m, 1H), 1.86-1.58 (m, 4H), 1.44-1.24 (m, 2H), 1.13 (d, J=6.3 Hz, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.58, -117.59. .sub.13C NMR (101 MHz, CDCl.sub.3) .delta. 160.94 (d, J=244.2 Hz), 139.81 (d, J=7.3 Hz), 134.60 (d, J=3.3 Hz), 128.53 (d, J=8.0 Hz), 116.78 (d, J=20.7 Hz), 112.84 (d, J=20.6 Hz), 70.25, 53.68, 38.03, 29.54, 27.08, 21.55, 20.55 (d, J=1.7 Hz), 18.16. IR (thin film) 3413, 2967, 1495, 1252, 1021, 955, 860 cm.sup.-1.

Example 3B: Preparation of (2R,3S)-4-ethyl-3-(4-fluoro-2-methylphenyl)hexan-2-ol

##STR00027##

[0099] A suspension of copper(I) iodide (401 mg, 2.106 mmol) in anhydrous diethyl ether (7.5 mL) was cooled to -30.degree. C. in a dry ice/acetonitrile bath. After -5 min, pentan-3-ylmagnesium bromide (2M in Et.sub.2O) (2106 .mu.L, 4.21 mmol) was added via syringe over 30 seconds, and the resulting solution was stirred at -30.degree. C. for 30 min, yielding a turbid dark grey/brown mixture. After 30 min, the reaction was cooled to -78.degree. C. in a dry ice/acetone bath, and (2R,3R)-2-(4-fluoro-2-methylphenyl)-3-methyloxirane (250 mg, 1.504 mmol) was added dropwise via syringe as a solution in diethyl ether (1.5 mL with 2.times.0.5 mL washes). The reaction was then stirred overnight, slowly warming to room temperature. TLC indicated consumption of starting material. The reaction was quenched with sat. aq. NH.sub.4Cl (20 mL) and extracted with diethyl ether (3.times.20 mL). The combined organic layers were dried over Na.sub.2SO.sub.4, filtered and concentrated to afford an oil. The oil was purified via silica gel Isco column chromatography (40 g silica gel column, 35 mL/min, 100% hexanes to 20% acetone:hexanes) to afford (2R,3S)-4-ethyl-3-(4-fluoro-2-methylphenyl)hexan-2-ol (116.7 mg, 0.490 mmol, 32.5% yield) as a yellow oil. .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.34 (dd, J=9.6, 6.1 Hz, 1H), 6.92-6.81 (m, 2H), 4.27 (dq, J=8.8, 4.7 Hz, 1H), 2.74 (dd, J=10.2, 3.6 Hz, 1H), 2.28 (s, 3H), 1.87 (qt, J=8.2, 3.6 Hz, 1H), 1.64 (dtd, J=14.9, 7.3, 4.4 Hz, 1H), 1.53 (tt, J=14.0, 6.7 Hz, 1H), 1.30-1.09 (m, 2H), 1.08-0.98 (m, 1H), 0.96 (d, J=6.4 Hz, 3H), 0.92 (t, J=7.5 Hz, 3H), 0.71 (t, J=7.4 Hz, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) d -118.01. .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 160.91 (d, J=243.7 Hz), 139.73 (d, J=7.1 Hz), 135.03 (d, J=3.3 Hz), 129.46 (d, J=7.9 Hz), 116.60 (d, J=20.5 Hz), 112.57 (d, J=20.4 Hz), 67.19, 47.45, 41.41, 22.08, 21.91, 21.53, 20.67 (d, J=1.6 Hz), 10.82, 9.78. IR (thin film) 3430, 2962, 1496, 1455, 1380, 1256, 956, 860, 801 cm.sup.-1.

Example 4A: Preparation of (2R,3S)-3-(4-fluoro-2-methylphenyl)-4-methylpent-4-en-2-ol

##STR00028##

[0101] A suspension of copper(I) iodide (0.160 g, 0.842 mmol) in anhydrous diethyl ether (4.0 mL) was cooled to -20.degree. C. After .about.5 min, prop-1-en-2-ylmagnesium bromide (1M in 2-Me-THF) (1.685 mL, 1.685 mmol) was added via syringe over 30 seconds, and the resulting solution was stirred at -20.degree. C. for 30 min. After 30 min, the reaction was cooled to -78.degree. C. and (2R,3R)-2-(4-fluoro-2-methylphenyl)-3-methyloxirane (0.100 g, 0.602 mmol) was added dropwise via syringe as a solution in diethyl ether (1.0 mL with 2.times.0.5 mL washes). The reaction was then stirred overnight, slowly warming to room temperature. TLC indicated consumption of starting material. The reaction was quenched with sat. aq. NH.sub.4Cl (20 mL) and extracted with diethyl ether (3.times.20 mL). The combined organic layers were dried over Na.sub.2SO.sub.4, filtered and concentrated to afford an oil. The oil was purified via silica gel Isco column chromatography (40 g silica gel column, 35 mL/min, 100% hexanes to 20% acetone:hexanes) to afford (2R,3S)-3-(4-fluoro-2-methylphenyl)-4-methylpent-4-en-2-ol (120.2 mg, 0.577 mmol, 96% yield) as a pale yellow oil. .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.37-7.30 (m, 1H), 6.93-6.86 (m, 2H), 4.89 (s, 2H), 4.32 (dq, J=8.8, 6.1 Hz, 1H), 3.42 (d, J=8.7 Hz, 1H), 2.34 (s, 3H), 1.59 (s, 3H), 1.52 (s, 1H), 1.30 (d, J=6.1 Hz, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -116.95. .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 161.27 (d, J=244.8 Hz), 144.85, 140.40 (d, J=7.5 Hz), 133.79 (d, J=3.2 Hz), 128.19 (d, J=8.2 Hz), 117.47 (d, J=20.6 Hz), 113.12, 112.76 (d, J=20.8 Hz), 68.13, 56.04, 21.28, 21.22, 20.03 (d, J=1.5 Hz). IR (thin film) 3373, 2970, 1495, 1240, 958, 861 cm.sup.-1.

Example 4B: Preparation of (2R,3S)-3-(4-fluoro-2-methylphenyl)-4-methylpentan-2-ol

##STR00029##

[0103] To a 20 mL vial containing (2R,3S)-3-(4-fluoro-2-methylphenyl)-4-methylpent-4-en-2-ol (120.2 mg, 0.577 mmol) and palladium on carbon (5%) (184 mg, 0.087 mmol) was added ethyl acetate (2886 .mu.L). The black reaction mixture was flushed with H.sub.2 gas via balloon. The resulting reaction was stirred at room temperature for 2 h, at which point TLC/UPLC indicated consumption of starting material. The reaction was filtered through a plug of celute, eluting with ethyl acetate (2.times.10 mL). The resulting solution was concentrated to afford an oil that was loaded directly onto a 25 g prepacked silica column in a minimal amount of dichloromethane and purified using Isco silica gel column chromatography (40 column, 40 mL/min, 100% hexanes to 30% ethyl acetate:hexanes) to afford (2R,3S)-3-(4-fluoro-2-methylphenyl)-4-methylpentan-2-ol (44.9 mg, 0.214 mmol, 37.0% yield) as a clear, colorless oil. .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.32 (dd, J=9.5, 6.1 Hz, 1H), 6.93-6.84 (m, 2H), 4.28 (qd, J=6.3, 4.4 Hz, 1H), 2.50 (dd, J=9.2, 4.4 Hz, 1H), 2.28 (s, 3H), 2.15 (dp, J=9.1, 6.6 Hz, 1H), 1.42-1.13 (m, 1H), 1.06 (d, J=6.6 Hz, 3H), 1.01 (d, J=6.3 Hz, 3H), 0.70 (d, J=6.7 Hz, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 160.93 (d, J=243.8 Hz), 139.78 (d, J=7.2 Hz), 134.96 (d, J=3.3 Hz), 129.17 (d, J=8.0 Hz), 116.64 (d, J=20.4 Hz), 112.57 (d, J=20.4 Hz), 67.70, 52.62, 30.26, 21.76, 21.32, 20.77. .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.97.

Example 4C: Preparation of (2R,3S)-3-(4-fluoro-2-methylphenyl)-4-methylpentan-2-ol

##STR00030##

[0105] To a 250 mL round bottom flask containing (2R,3S)-3-(4-fluoro-2-methylphenyl)-4-methylpent-4-en-2-ol (1.16 g, 5.57 mmol) and Wilkinson's catalyst (1.288 g, 1.392 mmol) was added THF (55.7 ml). The reddish-brown reaction mixture was flushed with H.sub.2 gas via balloon. The resulting reaction was stirred at room temperature overnight. The reaction was concentrated to a dark orange-brown oil, and the resulting oil was loaded directly onto a 25 g prepacked silica column in a minimal amount of dichloromethane and purified using Isco silica gel column chromatography (120 column, 85 mL/min, 100% hexanes to 30% ethyl acetate:hexanes) to afford (2R,3S)-3-(4-fluoro-2-methylphenyl)-4-methylpentan-2-ol (880 mg, 4.18 mmol, 75% yield) as a clear, colorless oil. .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.32 (dd, J=9.5, 6.0 Hz, 1H), 6.92-6.84 (m, 2H), 4.28 (qd, J=6.3, 4.4 Hz, 1H), 2.50 (dd, J=9.2, 4.4 Hz, 1H), 2.28 (s, 3H), 2.15 (ddd, J=13.2, 6.8, 2.3 Hz, 1H), 1.31-1.17 (m, 1H), 1.06 (d, J=6.6 Hz, 3H), 1.01 (d, J=6.3 Hz, 3H), 0.70 (d, J=6.7 Hz, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 160.92 (d, J=243.8 Hz), 139.78 (d, J=7.2 Hz), 134.95 (d, J=3.2 Hz), 129.16 (d, J=7.8 Hz), 116.64 (d, J=20.4 Hz), 112.57 (d, J=20.3 Hz), 67.70, 52.62, 30.26, 21.76, 21.31, 20.76. .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.97.

Example 5: Preparation of (3S)-4-ethyl-3-phenylhexan-2-ol

Step 1: Preparation of (2R,3S)-4-ethyl-3-phenylhexan-2-ol

##STR00031##

[0107] To a suspension of copper (I) iodide (667 mg, 3.50 mmol) in Et.sub.2O (12.5 mL) cooled to -78.degree. C. was added pentan-3-ylmagnesium bromide (2M in THF) (3.5 mL, 7.00 mmol). The reaction was warmed to -20.degree. C. and stirred at that temperature for 30 min. The reaction was then cooled to -78.degree. C. followed by the addition of (2R,3R)-2-methyl-3-phenyloxirane (335 mg, 2.5 mmol). The reaction was slowly warmed to room temperature and stirred overnight. The reaction was quenched by the addition of aqueous saturated NH.sub.4Cl. The mixture was filtered through a pad of Celite, and the solution was extracted with Et.sub.2O. The combined organic phases were dried over Na.sub.2SO.sub.4, filtered and concentrated under reduced pressure. The residue was purified by silica gel chromatography using a 0-10% acetone/hexane mixture as the eluent to provide the title compound as colorless oil (200 mg, 27%). .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.37-7.18 (m, 5H), 4.38-4.19 (m, 1H), 2.47 (dd, J=8.5, 5.1 Hz, 1H), 1.81 (ttd, J=8.8, 5.9, 3.2 Hz, 1H), 1.55-1.25 (m, 3H), 1.20 (d, J=5.6 Hz, 1H), 1.05 (d, J=6.3 Hz, 3H), 1.03-0.94 (m, 1H), 0.93 (t, J=7.4 Hz, 3H), 0.76 (t, J=7.4 Hz, 3H). ESIMS (m/z) 413 [2M+H].sup.+.

Step 2: Preparation of (S)-4-ethyl-3-phenylhexan-2-one

##STR00032##

[0109] To a solution containing (2R,3S)-4-ethyl-3-phenylhexan-2-ol (190 mg, 0.921 mmol) dissolved in CH.sub.2Cl.sub.2 (4.6 mL) at 0.degree. C. was added sodium bicarbonate (774 mg, 9.21 mmol) followed by Dess-Martin periodinane (781 mg, 1.842 mmol). The reaction was slowly warmed to room temperature over 3 hr. The reaction was quenched by the addition of aqueous saturated NaHCO.sub.3 solution followed by extraction with CH.sub.2Cl.sub.2. The combined organic phases were dried over Na.sub.2SO.sub.4, filtered and concentrated under reduced pressure. The residue was purified by silica gel chromatography using a 0-5% acetone/hexane mixture as the eluent to provide the title compound as colorless oil (124 mg, 63%). .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.54-7.10 (m, 5H), 3.61 (d, J=10.8 Hz, 1H), 2.21 (dtt, J=11.1, 7.5, 3.9 Hz, 1H), 2.09 (s, 3H), 1.49-1.32 (m, 2H), 1.31-1.15 (m, 1H), 1.05-0.94 (m, 1H), 0.89 (t, J=7.4 Hz, 3H), 0.69 (t, J=7.4 Hz, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 208.87, 137.71, 128.98, 128.66, 127.12, 63.12, 41.13, 30.15, 22.76, 21.03, 10.46, 9.47.

Step 3: Preparation of (3S)-4-ethyl-3-phenylhexan-2-ol

##STR00033##

[0111] To a stirred solution containing (S)-4-ethyl-3-phenylhexan-2-one (120 mg, 0.587 mmol) and (R)-1-methyl-3,3-diphenylhexahydropyrrolo[1,2-c][1,3,2]oxazaborole (1 M in toluene) (58.7 .mu.L, 0.059 mmol) dissolved in toluene (5.9 mL) at -78.degree. C. was added BH.sub.3--SMe.sub.2 complex (61.3 .mu.L, 0.646 mmol) dropwise. The reaction was slowly warmed to room temperature and stirred overnight. The reaction was then quenched carefully with methanol (475 .mu.L, 11.75 mmol). The mixture was diluted with H.sub.2O and extracted with Et.sub.2O. The combined organic phases were dried over Na.sub.2SO.sub.4, filtered and concentrated under reduced pressure. The residue was purified by silica gel chromatography using a 0-10% acetone/hexane mixture as the eluent to provide the title compound as colorless oil (110 mg, 86%). .sup.1H NMR shows a 3.3:1 mixture of diastereomers with the desired product being the major diastereomer. .sup.1H NMR (major diastereomer) (300 MHz, CDCl.sub.3) .delta. 7.37-7.04 (m, 5H), 4.22 (dt, J=13.8, 6.3 Hz, 1H), 2.75 (t, J=7.5 Hz, 1H), 1.85-1.73 (m, 1H), 1.55-1.21 (m, 3H), 1.18 (d, J=7.8 Hz, 1H), 1.05 (d, J=6.3 Hz, 3H), 1.03-0.97 (m, 1H), 0.94 (t, J=7.4 Hz, 3H), 0.81 (t, J=7.4 Hz, 3H). ESIMS (m/z) 413 [2M+H]+.

Example 6: Preparation of (2S,3S)-3-(4-fluorophenyl)-4-methylpentan-2-ol

Step 1: Preparation of (2S)-2-(benzyloxy)-1-(4-fluorophenyl)propan-1-ol

##STR00034##

[0113] A round bottom flask was charged with (S)-2-(benzyloxy)propanal (1.0 g, 6.09 mmol) dissolved in anhydrous THF (6.77 mL). This solution was cooled in an ice bath under an atmosphere of N.sub.2 and was treated dropwise with (4-fluorophenyl)magnesium bromide (6.70 mL, 6.70 mmol). The reaction was monitored by TLC (20% EtOAc in hexanes) until the reaction was complete. The reaction mixture was poured into saturated NH.sub.4Cl and the phases separated. The aqueous phase was extracted with EtOAc. The organic fractions were dried with magnesium sulfate and concentrated under reduced pressure. The crude residue was purified by automated silica gel chromatography (0-25% EtOAc in hexanes) to provide (2S)-2-(benzyloxy)-1-(4-fluorophenyl)propan-1-ol (1.404 g, 5.34 mmol, 88% yield) as a colorless oil. .sup.1H NMR analysis showed the mixture to be a 2:1 mixture of diastereomers. HRMS-ESI (m/z) [M+Na]+ calcd for C.sub.16H.sub.17FO.sub.2Na, 283.1105; found, 283.1105.

Step 2: Preparation of (S)-2-(benzyloxy)-1-(4-fluorophenyl)propan-1-one

##STR00035##

[0115] A 100 mL round bottom flask was charged with CH.sub.2Cl.sub.2 (12.26 mL), and oxalyl chloride (0.519 mL, 5.93 mmol). This solution was cooled in a dry ice/acetone bath under an atmosphere of N.sub.2 and treated dropwise with DMSO (0.842 mL, 11.87 mmol). The resultant mixture was stirred for .about.2 minutes and then treated dropwise with a solution of (2S)-2-(benzyloxy)-1-(4-fluorophenyl)propan-1-ol (1.404 g, 5.39 mmol) in 3 mL of CH.sub.2Cl.sub.2 (extra rinse with 1 mL). After stirring for .about.15 minutes, the reaction mixture was treated dropwise with triethylamine (3.76 mL, 27.0 mmol). The reaction mixture was stirred for 5 minutes and then allowed to warm to room temperature. The reaction was monitored by TLC (20% EtOAc in hexanes). The reaction mixture was poured into H.sub.2O and the phases were separated. The aqueous phase was extracted with CH.sub.2Cl.sub.2. The combined organics were dried with sodium sulfate and concentrated. The crude residue was purified by silica gel chromatography (0-15% EtOAc in hexanes) to provide (S)-2-(benzyloxy)-1-(4-fluorophenyl)propan-1-one (1.1475 g, 4.44 mmol, 82% yield) as a colorless oil. .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.20-8.04 (m, 2H), 7.40-7.24 (m, 5H), 7.19-7.02 (m, 2H), 4.70 (q, J=6.9 Hz, 1H), 4.61 (d, J=11.6 Hz, 1H), 4.45 (d, J=11.6 Hz, 1H), 1.54 (d, J=6.9 Hz, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -104.39. .sup.13C NMR (126 MHz, CDCl.sub.3) .delta. 199.27, 165.83 (d, J=255.3 Hz), 137.41, 131.69 (d, J=9.2 Hz), 131.08 (d, J=2.9 Hz), 128.46, 127.98, 127.93, 115.71 (d, J=21.8 Hz), 78.72, 71.65, 18.81. HRMS-ESI (m/z) [M+Na]+ calcd for C.sub.16H.sub.15FO.sub.2Na, 281.0948; found, 281.0950.

[0116] Step 2A: Preparation of (S)-1-(benzo[d][1,3]dioxol-5-yl)-2-(benzyloxy)propan-1-one.

##STR00036##

[0117] To a vial charged with (S)-2-(benzyloxy)-1-(pyrrolidin-1-yl)propan-1-one (1 g, 4.29 mmol) dissolved in anhydrous THF (12 mL) was added dropwise benzo[d][1,3]dioxol-5-ylmagnesium bromide (1M in 1:1 toluene/THF, 4.29 mL, 4.29 mmol) at -5.degree. C. The mixture was allowed to warm to ambient temperature and stirred overnight. The mixture was quenched by the addition of 1 N HCl. The layers were separated, followed by extraction with ethyl ether (3.times.10 mL). The combined organic layers were washed with brine, dried over sodium sulfate, and concentrated in vacuo. The residue was purified via automated silica gel chromatography (Isco, 0-25% EtOAc/hexanes as the eluent) to afford (S)-1-(benzo[d][1,3]dioxol-5-yl)-2-(benzyloxy)propan-1-one (0.39 g, 30%) as yellow oil. .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 7.73 (dd, J=8.2, 1.7 Hz, 1H), 7.55 (d, J=1.6 Hz, 1H), 7.39-7.27 (m, 5H), 6.84 (d, J=8.2 Hz, 1H), 6.04 (s, 2H), 4.70 (q, J=6.9 Hz, 1H), 4.53 (dd, J=103.5, 11.6 Hz, 2H), 1.52 (d, J=6.9 Hz, 3H). .sup.13C NMR (126 MHz, CDCl.sub.3) .delta. 198.8, 152.0, 148.1, 137.6, 129.4, 128.4, 127.9, 127.8, 125.2, 108.6, 107.9, 101.8, 78.4, 71.5, 19.1. HRMS-ESI (m/z) [M+H]+ calcd for C.sub.17H.sub.17O.sub.4, 285.1121; found, 285.1121.

Step 3: Preparation of (2S)-2-(benzyloxy)-3-(4-fluorophenyl)-4-methylpentan-3-ol

##STR00037##

[0119] A solution of isopropylmagnesium bromide (1.936 mL, 3.87 mmol) was added to anhydrous THF (6.45 ml) cooled to 0.degree. C. in an ice bath. A solution of (S)-2-(benzyloxy)-1-(4-fluorophenyl)propan-1-one (0.5 g, 1.936 mmol) in THF (2 mL+1 mL to rinse the syringe) was added dropwise. The reaction was stirred until complete by consumption of starting material by TLC (20% EtOAc in hexanes). The reaction was quenched by the addition of saturated ammonium chloride and the mixture was extracted with EtOAc. The combined organic fractions were dried over MgSO.sub.4, filtered and concentrated. The crude residue was purified by automated silica gel chromatography (0-10% EtOAc in hexanes) to provide (2S)-2-(benzyloxy)-3-(4-fluorophenyl)-4-methylpentan-3-ol (201.9 mg, 0.634 mmol, 33% yield) as a white foam. .sup.1H NMR data showed a 9.2:1 ratio of diastereomers. .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.43-7.20 (m, 7H), 7.00 (t, J=8.8 Hz, 2H), 4.72 (d, J=11.4 Hz, 1H), 4.49 (d, J=11.5 Hz, 1H), 4.09 (q, J=6.2 Hz, 1H), 2.46 (s, 1H), 2.35 (p, J=6.8 Hz, 1H), 1.00 (d, J=6.2 Hz, 3H), 0.77 (dd, J=8.8, 6.8 Hz, 6H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.13. .sup.13C NMR (126 MHz, CDCl.sub.3) .delta. 161.55 (d, J=244.4 Hz), 138.28, 136.60 (d, J=3.2 Hz), 128.45, 128.14 (d, J=7.7 Hz), 127.80, 114.09 (d, J=20.9 Hz), 80.56, 70.91, 34.79, 17.93, 16.87, 13.63. HRMS-ESI (m/z) [M+Na]+ calcd for C.sub.19H.sub.23FO.sub.2Na, 325.1574; found, 325.1574.

Step 4: Preparation of 1-((2S,3S)-2-(benzyloxy)-4-methylpentan-3-yl)-4-fluorobenzene

##STR00038##

[0121] To a solution of (2S)-2-(benzyloxy)-3-(4-fluorophenyl)-4-methylpentan-3-ol (0.2 g, 0.661 mmol) dissolved in CH.sub.2Cl.sub.2 (2.205 ml) at 0.degree. C. was added triethylsilane (1.056 mL, 6.61 mmol) followed by trifluoroacetic acid (0.510 mL, 6.61 mmol). The mixture was stirred at 0.degree. C. for 1 hr. The mixture was then allowed to slowly warm to room temperature and stirred overnight. The reaction was carefully quenched by the addition of a saturated sodium bicarbonate solution and extracted with CH.sub.2Cl.sub.2. The combined organic layers were then dried over sodium sulfate, filtered and concentrated under reduced pressure. The crude residue was purified by automated silica gel chromatography (0-5% EtOAc in hexanes) to provide 1-((2S,3S)-2-(benzyloxy)-4-methylpentan-3-yl)-4-fluorobenzene (152.2 mg, 0.505 mmol, 76% yield) as a colorless oil. .sup.1H NMR data revealed a 7.2:1 ratio of diastereomers. .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.39-7.26 (m, 5H), 7.07-6.91 (m, 4H), 4.66 (d, J=11.6 Hz, 1H), 4.50 (d, J=11.6 Hz, 1H), 3.88 (dq, J=8.5, 6.1 Hz, 1H), 2.61 (d, J=14.4 Hz, 1H), 2.37 (dq, J=13.4, 6.7 Hz, 1H), 1.01 (d, J=6.1 Hz, 3H), 0.80 (d, J=6.8 Hz, 3H), 0.74 (d, J=6.8 Hz, 3H). .sup.13C NMR (126 MHz, CDCl.sub.3) .delta. 161.48 (d, J=243.8 Hz), 138.84, 135.66 (d, J=3.3 Hz), 131.08 (d, J=7.6 Hz), 128.35, 127.71, 127.49, 114.48 (d, J=20.8 Hz), 75.31, 70.71, 57.21, 27.57, 21.59, 18.36, 17.35. HRMS-ESI (m/z) [M+Na]+ calcd for C.sub.19H.sub.23FONa, 309.1625; found, 309.1629.

Step 5: Preparation of (2S,3S)-3-(4-fluorophenyl)-4-methylpentan-2-ol

##STR00039##

[0123] A flask containing 1-((2S)-2-(benzyloxy)-4-methylpentan-3-yl)-4-fluorobenzene (0.15 g, 0.524 mmol) was charged with 5% palladium on carbon (0.056 g, 0.026 mmol) and then suspended in ethanol (2.62 mL). The reaction atmosphere was replaced with hydrogen gas via a balloon (1 atm) and monitored until complete by TLC (25% EtOAc in hexanes). The reaction was filtered through a pad of Celite.COPYRGT. and the pad was washed with ethyl acetate. The filtrate was concentrated under reduced pressure. The crude residue was purified by automated column chromatography (0-20% EtOAc in hexanes as the eluent) to provide (2S,3S)-3-(4-fluorophenyl)-4-methylpentan-2-ol (76.9 mg, 0.388 mmol, 74.1% yield) as a white foam. .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 7.11-7.05 (m, 2H), 7.03-6.97 (m, 2H), 4.17 (dq, J=7.5, 6.2 Hz, 1H), 2.47 (t, J=7.5 Hz, 1H), 2.18 (dp, J=13.6, 6.8 Hz, 1H), 1.19 (d, J=7.2 Hz, 1H), 1.03 (d, J=6.3 Hz, 3H), 0.90 (d, J=6.7 Hz, 3H), 0.79 (d, J=6.7 Hz, 3H). .sup.13C NMR (126 MHz, CDCl.sub.3) .delta. 161.65 (d, J=244.4 Hz), 135.15 (d, J=3.4 Hz), 131.11 (d, J=7.6 Hz), 114.76 (d, J=20.9 Hz), 68.13, 59.08, 28.28, 21.34, 20.53, 19.47. IR (thin film) 3348, 2960, 2929, 2872, 1604, 1508, 1465, 1368, 1223, 1160, 833 cm.sup.-1.

Step 6: Preparation of (4S)-4-(benzyloxy)-3-(4-fluorophenyl)-2-methylpent-1-en-3-ol

##STR00040##

[0125] To a solution containing prop-1-en-2-ylmagnesium bromide (1 M in 2-Me-THF) (4.29 mL, 4.29 mmol) dissolved in THF (21.44 mL) and cooled to 0.degree. C. in an ice/water bath was added (S)-2-(benzyloxy)-1-(4-fluoro-3-methylphenyl)propan-1-one (0.584 g, 2.144 mmol) dropwise over 5 minutes as a solution in THF (3 mL). The resulting solution was stirred for 1 hr, at which point an additional 2.1 mL (1 equivalent) of the Grignard reagent was added, and the reaction was stirred for an additional hour. The reaction was quenched with saturated aqueous NH.sub.4Cl (50 mL) solution and extracted with EtOAc (3.times.50 mL). The combined organic layers were dried over Na.sub.2SO.sub.4, filtered, and concentrated to an oil. The oil was loaded onto a prepacked 25 g silica gel column and purified using Isco silica gel column chromatography (40 column, 35 mL/min, 100% hexanes to 20% ethyl acetate:hexanes) to afford the title compound (671 mg, 100%) as a clear, colorless oil. .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.40-7.23 (m, 6H), 7.16 (ddd, J=7.9, 4.9, 2.4 Hz, 1H), 6.92 (t, J=9.0 Hz, 1H), 5.17 (t, J=1.0 Hz, 1H), 4.98 (p, J=1.4 Hz, 1H), 4.69 (d, J=11.4 Hz, 1H), 4.51 (d, J=11.4 Hz, 1H), 4.21 (q, J=6.1 Hz, 1H), 2.81 (s, 1H), 2.26 (d, J=1.9 Hz, 3H), 1.63 (t, J=1.0 Hz, 3H), 0.99 (d, J=6.1 Hz, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) d -120.68. IR (thin film) 3500, 2977, 2923, 1499, 1242, 1114, 1097, 894, 818, 733, 697 cm.sup.-1. HRMS-ESI (m/z) [M+H]+ calcd for C.sub.20H.sub.23FNaO.sub.2, 337.1574; found, 337.1584.

Step 7: Preparation of (2S)-2-(benzyloxy)-3-(4-fluorophenyl)-4-methylpentan-3-ol

##STR00041##

[0127] A solution containing (3S,4S)-4-(benzyloxy)-3-(4-fluoro-3-methylphenyl)-2-methylpent-1-en-3-ol (0.6713 g, 2.135 mmol) and Wilkinson's catalyst (0.593 g, 0.641 mmol) dissolved in THF (14.23 mL) was flushed with hydrogen gas via balloon. The resulting reaction was stirred at room temperature overnight. The reaction mixture was concentrated to a dark orange-brown oil under reduced pressure. The resulting oil was loaded directly onto a 25 g prepacked silica column in a minimal amount of dichloromethane and purified using Isco silica gel column chromatography (40 column, 35 mL/min, 100% hexanes to 20% ethyl acetate:hexanes) to afford the title compound (659 mg, 98%) as a clear, colorless oil. .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.41-7.28 (m, 5H), 7.16 (dd, J=7.6, 2.3 Hz, 1H), 7.05 (ddd, J=7.8, 5.0, 2.4 Hz, 1H), 6.92 (t, J=9.0 Hz, 1H), 4.72 (d, J=11.4 Hz, 1H), 4.49 (d, J=11.4 Hz, 1H), 4.08 (q, J=6.2 Hz, 1H), 2.44 (s, 1H), 2.34 (p, J=6.8 Hz, 1H), 2.27 (d, J=1.9 Hz, 3H), 1.01 (d, J=6.1 Hz, 3H), 0.77 (dd, J=10.6, 6.8 Hz, 6H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -121.44. .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 160.12 (d, J=243.5 Hz), 138.39, 136.31 (d, J=3.5 Hz), 129.74 (d, J=4.9 Hz), 128.45, 127.79, 127.75, 125.35 (d, J=7.8 Hz), 123.40 (d, J=17.0 Hz), 113.69 (d, J=22.1 Hz), 80.55, 77.07, 70.95, 34.84, 18.01, 16.94, 14.80 (d, J=3.5 Hz), 13.71. IR (thin film) 3564, 2962, 2935, 1501, 1374, 1243, 1105, 1089, 817, 757, 697 cm.sup.-1. HRMS-ESI (m/z) [M+H]+ calcd for C.sub.20H.sub.25FNaO.sub.2, 339.1731; found, 339.1728.

Example 6A: Preparation of (2R,3S)-3-(2,5-dimethylphenyl)-4-methylpentan-2-ol

Step 1: Preparation of 2-(2,5-dimethylphenyl)-3-methylbutanoic acid

##STR00042##

[0129] A solution of isopropylmagnesium chloride (2 M in THF, 5.79 mL, 11.57 mmol) was added slowly to a solution of 2-(2,5-dimethylphenyl)acetic acid (0.95 g, 5.79 mmol) in THF (11.57 mL) at room temperature. The resulting thick suspension was stirred for 1 hr and treated with 2-iodopropane (1.736 mL, 17.36 mmol). The reaction was heated to 70.degree. C. and stirred overnight. The reaction was quenched by the addition of 1N HCl and extracted with EtOAc. The organic layer was dried over magnesium sulfate, filtered and concentrated under reduced pressure. The residue was purified by automated column chromatography (Isco, 0-30% EtOAc in hexanes as the eluent) to provide 2-(2,5-dimethylphenyl)-3-methylbutanoic acid (670 mg, 53.3%) as a white solid. .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 11.32 (bs, 1H), 7.21 (s, 1H), 7.04 (d, J=7.7 Hz, 1H), 6.95 (d, J=8.5 Hz, 1H), 3.46 (d, J=10.9 Hz, 1H), 2.40-2.34 (m, 1H), 2.33 (s, 3H), 2.29 (s, 3H), 1.11 (d, J=6.4 Hz, 3H), 0.69 (d, J=6.7 Hz, 3H). .sup.13C NMR (126 MHz, CDCl.sub.3) .delta. 179.72, 136.08, 135.79, 133.69, 130.22, 127.82, 127.67, 54.23, 31.46, 21.62, 21.12, 19.75, 19.69. HRMS-ESI (m/z) [2M+H]+ calcd for C.sub.13H.sub.18O.sub.2, 413.2686; found, 413.2674.

Step 2: Preparation of 2-(2,5-dimethylphenyl)-N-methoxy-N,3-dimethylbutanamide

##STR00043##

[0131] To a solution containing 2-(2,5-dimethylphenyl)-3-methylbutanoic acid (0.66 g, 3.20 mmol) dissolved in 32 mL of CH.sub.2Cl.sub.2 at 0.degree. C. was added 4-methylmorpholine (0.70 mL, 6.40 mmol) and N,O-dimethylhydroxylamine hydrochloride (0.624 g, 5.71 mmol). 3-(((Ethylimino)methylene)amino)-N,N-dimethylpropan-1-amine hydrochloride (EDC, 1.23 g, 6.40 mmol) was added and the reaction was warmed to room temperature and stirred overnight. The reaction was concentrated under reduced pressure and the residue was purified by automated silica gel chromatography (Isco, 0-25% EtOAc in hexanes as the eluent) to provide 2-(2,5-dimethylphenyl)-N-methoxy-N,3-dimethylbutanamide (694 mg, 83%) as a colorless oil. .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 7.27 (s, 1H), 7.01 (d, J=7.7 Hz, 1H), 6.93-6.89 (m, 1H), 3.84 (d, J=10.3 Hz, 1H), 3.48 (s, 3H), 3.14 (s, 3H), 2.41-2.35 (m, 1H), 2.34 (s, 3H), 2.27 (s, 3H), 1.05 (d, J=6.4 Hz, 3H), 0.68 (d, J=6.8 Hz, 3H). .sup.13C NMR (126 MHz, CDCl.sub.3) .delta. 137.49, 135.69, 133.14, 129.89, 127.88, 127.23, 60.95, 49.90, 32.65, 32.21, 22.25, 21.11, 19.51. HRMS-ESI (m/z) [M+H]+ calcd for C.sub.15H.sub.23NO.sub.2, 250.1802; found, 250.1799.

Step 3: Preparation of 3-(2,5-dimethylphenyl)-4-methylpentan-2-one

##STR00044##

[0133] A solution containing 2-(2,5-dimethylphenyl)-N-methoxy-N,3-dimethylbutanamide (0.685 g, 2.75 mmol) dissolved in THF (18.31 mL) was cooled to 0.degree. C. Methylmagnesium bromide (3.0 M in diethyl ether, 2.75 ml, 8.24 mmol) was added dropwise and the reaction was allowed to warm to room temperature and stirred overnight. The reaction was quenched by the addition of saturated ammonium chloride solution and was extracted with EtOAc. The organic layer was dried over magnesium sulfate, filtered and concentrated under reduced pressure to provide 3-(2,5-dimethylphenyl)-4-methylpentan-2-one (573.3 mg, 97%) as a yellow oil. .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 7.27 (s, 1H), 7.06 (d, J=7.6 Hz, 1H), 6.94 (d, J=7.7 Hz, 1H), 3.58 (d, J=10.5 Hz, 1H), 2.44-2.38 (m, 1H), 2.37 (s, 3H), 2.27 (s, 3H), 2.02 (s, 3H), 1.01 (d, J=6.4 Hz, 3H), 0.65 (d, J=6.8 Hz, 3H). .sup.13C NMR (126 MHz, CDCl.sub.3) .delta. 208.55, 136.24, 135.95, 133.52, 130.48, 127.83, 127.61, 62.29, 30.53, 30.09, 21.86, 21.04, 19.91, 19.51. HRMS-ESI (m/z) [M+H]+ calcd for C.sub.14H.sub.20O, 205.1587; found, 205.1578.

Step 4: Preparation of (2R,3S)-3-(2,5-dimethylphenyl)-4-methylpentan-2-ol and (2S,3R)-3-(2,5-dimethylphenyl)-4-methylpentan-7-ol

##STR00045##

[0135] Lithium aluminum hydride (2.80 mL, 2.80 mmol) as a solution (1.0 M in THF) was added to a flask containing THF (28.0 mL) cooled to -78.degree. C. A solution of 3-(2,5-dimethylphenyl)-4-methylpentan-2-one (0.573 g, 2.80 mmol) in THF (3 mL) was added dropwise. The reaction was warmed to room temperature and stirred overnight. The reaction was cooled to 0.degree. C. and quenched by the addition of 0.1 mL H.sub.2O, 0.1 mL 1N NaOH, followed by an additional 0.3 mL of H.sub.2O. The mixture was stirred vigorously for 15 min. The reaction was filtered and the solids were washed with EtOAc. The filtrate was concentrated under reduced pressure to provide a racemic mixture of (2R,3S)-3-(2,5-dimethylphenyl)-4-methylpentan-2-ol and (2S,3R)-3-(2,5-dimethylphenyl)-4-methylpentan-2-ol (491 mg, 72%) as a colorless oil. The syn product is the exclusive product as predicted by Cram's rule. .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 7.12 (s, 1H), 7.05 (d, J=7.7 Hz, 1H), 6.94-6.91 (m, 1H), 4.32-4.20 (m, 1H), 2.55 (dd, J=8.9, 4.7 Hz, 1H), 2.31 (s, 3H), 2.25 (s, 3H), 2.17 (ddt, J=13.3, 8.8, 6.7 Hz, 1H), 1.26 (d, J=6.1 Hz, 1H), 1.05 (d, J=2.3 Hz, 3H), 1.04 (d, J=2.0 Hz, 3H), 0.72 (d, J=6.7 Hz, 3H). .sup.13C NMR (126 MHz, CDCl.sub.3) .delta. 138.84, 135.13, 134.66, 130.18, 128.14, 126.71, 67.91, 62.20, 53.16, 30.01, 21.76, 21.36, 20.75, 20.29. ESIMS (m/z) 207 [M+H]+.

Step 5: Preparation of (2R,3S) and (2S,3R)-3-(2,5-dimethylphenyl)-4-methylpentan-2-yl (S)-2-methoxy-2-phenylacetate

##STR00046##

[0137] To a racemic mixture containing (2R,3S) and (2S,3R)-3-(2,5-dimethylphenyl)-4-methylpentan-2-ol (0.491 g, 2.380 mmol) dissolved in 16 mL of CH.sub.2Cl.sub.2 was added N,N-dimethylpyridin-4-amine (0.029 g, 0.238 mmol) and (S)-2-methoxy-2-phenylacetic acid (0.514 g, 3.09 mmol). The reaction was cooled to 0.degree. C. followed by addition of 3-(((ethylimino)methylene)amino)-N,N-dimethylpropan-1-amine hydrochloride (0.912 g, 4.76 mmol) was added and the reaction was warmed to room temperature and stirred overnight. The mixture was concentrated under reduced pressure. The residue was purified by automated silica gel chromatography (Isco, 80 g SiO.sub.2 column, 0-10% MTBE in hexanes as the eluent) to provide (2R,3S)-3-(2,5-dimethylphenyl)-4-methylpentan-2-yl (S)-2-methoxy-2-phenylacetate (284.7 mg 32%) and (2S,3R)-3-(2,5-dimethylphenyl)-4-methylpentan-2-yl (S)-2-methoxy-2-phenylacetate as colorless oils. Only the desired (2R,3S) diastereomer was characterized. .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 7.44-7.37 (m, 2H), 7.36-7.27 (m, 3H), 7.18 (s, 1H), 7.00 (d, J=7.7 Hz, 1H), 6.93-6.80 (m, 1H), 5.42-5.34 (m, 1H), 4.74 (s, 1H), 3.40 (s, 3H), 2.62 (dd, J=9.7, 4.3 Hz, 1H), 2.30 (s, 3H), 2.21 (s, 3H), 2.05-1.92 (m, 1H), 0.93 (d, J=6.5 Hz, 3H), 0.87 (d, J=6.3 Hz, 3H), 0.68 (d, J=6.7 Hz, 3H). .sup.13C NMR (126 MHz, CDCl.sub.3) .delta. 170.32, 139.03, 136.46, 134.96, 133.92, 129.67, 128.80, 128.51, 126.90, 126.67, 82.86, 72.23, 57.31, 51.06, 30.54, 21.31, 21.00, 20.93, 20.23, 17.82. HRMS-ESI (m/z) [M+Na]+ calcd for C.sub.23H.sub.30O.sub.3, 377.2087; found, 377.2089.

Step 6: Preparation of (2R,3S)-3-(2,5-dimethylphenyl)-4-methylpentan-2-ol

##STR00047##

[0139] To a solution containing (2R,3S)-3-(2,5-dimethylphenyl)-4-methylpentan-2-yl(S)-2-methoxy-2-phenyla- cetate (0.28 g, 0.790 mmol) dissolved in MeOH (7.90 mL) was added potassium carbonate (0.327 g, 2.370 mmol). The reaction was heated to 55.degree. C. and stirred overnight. The reaction was cooled to room temperature, diluted with water and extracted with CH.sub.2Cl.sub.2. The combined organic layers were dried over sodium sulfate, filtered and concentrated under reduced pressure. The crude material was purified by automated silica gel chromatography (Isco, 0-20% EtOAc in hexanes as the eluent) to provide (2R,3S)-3-(2,5-dimethylphenyl)-4-methylpentan-2-ol (139 mg, 81%) as a colorless oil. .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 7.12 (s, 1H), 7.05 (d, J=7.7 Hz, 1H), 6.96-6.87 (m, 1H), 4.33-4.19 (m, 1H), 2.55 (dd, J=8.9, 4.7 Hz, 1H), 2.31 (s, 3H), 2.25 (s, 3H), 2.17 (ddt, J=13.4, 8.8, 6.7 Hz, 1H), 1.26 (d, J=6.1 Hz, 1H), 1.05 (d, J=2.1 Hz, 3H), 1.04 (d, J=1.8 Hz, 3H), 0.72 (d, J=6.7 Hz, 3H). IR (thin film) 3429 (b), 2956, 2925, 2868, 1500, 1457, 1382, 1151, 1027, 905, 806, 787 cm.sup.-1. HRMS-ESI (m/z) [M+NH.sub.4]+ calcd for C.sub.14H.sub.22O, 224.2009; found, 224.2001.

Example 7: Preparation of (2S,3S)-3-(4-fluoro-2-methylphenyl)-4-methylpentan-2-ol

Step 1: Preparation of (2S,3S)-3-(4-fluoro-2-methylphenyl)-4-methylpentan-2-yl 4-nitrobenzoate

##STR00048##

[0141] In a 250 mL round bottom flask, a solution of (2R,3S)-3-(4-fluoro-2-methylphenyl)-4-methylpentan-2-ol (0.880 g, 4.18 mmol), triphenylphosphine (4.17 g, 15.90 mmol) and 4-nitrobenzoic acid (2.87 g, 17.16 mmol) was prepared in anhydrous THF (41.8 ml) and cooled to 0.degree. C. in an ice/water bath. After .about.5 min, diethyl (E)-diazene-1,2-dicarboxylate (2.97 ml, 18.83 mmol) was added dropwise, and the mixture was allowed to slowly warm to room temperature overnight. After 18 hr, TLC indicated .about.75% conversion to a single higher R.sub.f spot. The reaction was then heated to 40.degree. C. and stirred for an additional 12 hr. The mixture was cooled to room temperature and quenched with a saturated aqueous solution of NH.sub.4Cl (40 mL) and extracted with CH.sub.2Cl.sub.2 (3.times.40 mL). The combined organic layers were passed through a phase separator and concentrated to an oil. The residue was purified via silica gel Isco column chromatography (80 g silica gel column, 60 mL/min, 100% hexanes to 20% acetone:hexanes) to afford (2S,3S)-3-(4-fluoro-2-methylphenyl)-4-methylpentan-2-yl 4-nitrobenzoate (1.34 g, 3.73 mmol, 89% yield) as a yellow oil. .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.33-8.26 (m, 2H), 8.17-8.11 (m, 2H), 7.14 (dd, J=9.5, 5.9 Hz, 1H), 6.98-6.86 (m, 2H), 5.65 (dq, J=8.2, 6.3 Hz, 1H), 3.18 (t, J=7.8 Hz, 1H), 2.30 (s, 3H), 2.19-2.09 (m, 1H), 1.19 (d, J=6.3 Hz, 3H), 0.98 (d, J=6.7 Hz, 3H), 0.80 (d, J=6.8 Hz, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.11. IR (thin film) 3353, 2961, 1719, 1528, 1277, 1102, 720 cm.sup.-1. ESIMS (m/z) 359.1 [M+H].sup.+.

Step 2: Preparation of (2S,3S)-3-(4-fluoro-2-methylphenyl)-4-methylpentan-2-ol

##STR00049##

[0143] In a 250 mL round-bottom flask, a solution of (2S,3S)-3-(4-fluoro-2-methylphenyl)-4-methylpentan-2-yl 4-nitrobenzoate (1.34 g, 3.73 mmol) was prepared in THF (49.7 mL) and cooled to 0.degree. C. in an ice/water bath. After .about.5 min, sodium hydroxide (10% aqueous solution) (44 mL, 3.73 mmol) (39.7 mL water+4.4 mL 50% w/w/NaOH) was added dropwise, and the mixture was allowed to slowly warm to room temperature over 1 hr and then heated to 40.degree. C. and stirred for 2 days. The reaction was cooled to ambient temperature. The reaction was quenched by the addition of a saturated aqueous solution of NH.sub.4Cl (100 mL) and extracted with CH.sub.2Cl.sub.2 (3.times.100 mL). Additional product remained in aqueous layer as evidenced by TLC, so 100 mL brine was added to aqueous layer, and the aqueous layer was extracted again with CH.sub.2Cl.sub.2 (2.times.100 mL), after which no additional product was observed in the aqueous layer. The combined organic layers were then passed through a phase separator and concentrated to afford an oil that was purified via silica gel Isco column chromatography (120 g silica gel column, 85 mL/min, 100% hexanes to 30% acetone:hexanes) to afford (2S,3S)-3-(4-fluoro-2-methylphenyl)-4-methylpentan-2-ol (460 mg, 2.187 mmol, 58.7% yield) (52% over 2 steps) as a clear, colorless oil. .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.02 (dd, J=8.6, 6.0 Hz, 1H), 6.94-6.81 (m, 2H), 4.25-4.12 (m, 1H), 2.88 (t, J=7.6 Hz, 1H), 2.35 (s, 3H), 2.25-2.12 (m, 1H), 1.21 (d, J=6.0 Hz, 1H), 1.04 (d, J=6.3 Hz, 3H), 0.94 (d, J=6.7 Hz, 3H), 0.80 (d, J=6.7 Hz, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.86. .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 160.86 (d, J=243.9 Hz), 140.35 (d, J=7.4 Hz), 134.42 (d, J=3.1 Hz), 129.29 (d, J=6.8 Hz), 116.88 (d, J=20.3 Hz), 112.20 (d, J=20.6 Hz), 69.48, 29.72, 21.12, 21.00, 20.99, 20.65, 19.98. IR (thin film) 3382, 2960, 2927, 1716, 1497, 1365, 1225, 736 cm.sup.-1.

Example 8: (2S,3S)-3-(4-fluorophenyl)-4-methylpentan-2-yl(tert-butoxycarbo- nyl)-L-alaninate

##STR00050##

[0145] To a stirred solution of (2S,3S)-3-(4-fluorophenyl)-4-methylpentan-2-ol (0.075 g, 0.382 mmol), (tert-butoxycarbonyl)-L-alanine (0.108 g, 0.573 mmol) and DMAP (4.67 mg, 0.038 mmol) dissolved in CH.sub.2Cl.sub.2 (3.82 mL) at 0.degree. C. in an ice bath was added N.sup.1-((ethylimino)methylene)-N.sup.3,N.sup.3-dimethylpropane-1,3-diami- ne hydrochloride (EDC; 0.147 g, 0.764 mmol) and the reaction was monitored until complete by TLC (25% EtOAc in hexanes). The reaction was purified by automated column chromatography (0-10% EtOAc in hexanes) to provide (2S,3S)-3-(4-fluorophenyl)-4-methylpentan-2-yl (tert-butoxycarbonyl)-L-alaninate (137.5 mg, 0.370 mmol, 97% yield) as colorless oil. .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.06 (dd, J=8.7, 5.6 Hz, 2H), 7.02-6.92 (m, 2H), 5.36 (dq, J=8.7, 6.3 Hz, 1H), 5.05 (s, 1H), 4.37-4.19 (m, 1H), 2.69 (dd, J=8.7, 6.4 Hz, 1H), 2.08 (h, J=6.7 Hz, 1H), 1.45 (s, 9H), 1.38 (d, J=7.2 Hz, 3H), 1.06 (d, J=6.2 Hz, 3H), 0.86 (d, J=6.8 Hz, 3H), 0.74 (d, J=6.8 Hz, 3H). .sup.13C NMR (126 MHz, CDCl.sub.3) .delta. 172.79, 161.75 (d, J=244.8 Hz), 155.03, 134.29, 131.03 (d, J=7.6 Hz), 114.82 (d, J=21.0 Hz), 79.79, 72.32, 55.88, 49.50, 28.34, 28.18, 21.30, 18.81, 18.41, 17.74. IR (thin film) 3352, 2964, 2932, 1712, 1605, 1509, 1452, 1366, 1224, 1160, 835 cm.sup.-1. HRMS-ESI (m/z) [M+Na]+ calcd for C.sub.20H.sub.30FNNaO.sub.4, 390.2051; found, 390.2044.

Example 9: Preparation of (2S,3S)-3-(4-fluoro-2-methylphenyl)-4-methylpentan-2-yl (tert-butoxycarbonyl)-L-alaninate

##STR00051##

[0147] In a small vial, (2R,3S)-3-(4-fluoro-2-methylphenyl)-4-methylpentan-2-ol (115.5 mg, 0.549 mmol), (tert-butoxycarbonyl)-L-alanine (125 mg, 0.659 mmol) and triphenylphosphine (173 mg, 0.659 mmol) were dissolved in THF (2.75 mL) under a N.sub.2 atmosphere and cooled to 0.degree. C. in an ice/water bath. After .about.5 min, diisopropyl (E)-diazene-1,2-dicarboxylate (130 .mu.L, 0.659 mmol) was added in dropwise via syringe over 3 min, and the resulting pale orange reaction was stirred overnight, slowly warming to room temperature as the ice melted. After 18 hr, the reaction was concentrated under reduced pressure to afford an oil. The oil was loaded directly onto a 12 g prepacked silica column in a minimal amount of dichloromethane and purified using Isco silica gel column chromatography (120 column, 85 mL/min, 100% pet ether to 40% MTBE:pet ether) to afford (2S,3S)-3-(4-fluoro-2-methylphenyl)-4-methylpentan-2-yl (tert-butoxycarbonyl)-L-alaninate (35.0 mg, 0.092 mmol, 17% yield) as a clear, colorless oil. .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.05 (dd, J=8.5, 6.0 Hz, 1H), 6.87 (ddt, J=11.6, 8.3, 4.1 Hz, 2H), 5.33 (dq, J=9.1, 6.2 Hz, 1H), 5.05 (d, J=8.1 Hz, 1H), 4.28 (d, J=7.6 Hz, 1H), 3.08 (dd, J=9.2, 6.2 Hz, 1H), 2.32 (s, 3H), 2.18-2.06 (m, 1H), 1.45 (s, 9H), 1.39 (d, J=7.2 Hz, 3H), 1.03 (d, J=6.2 Hz, 3H), 0.85 (d, J=6.8 Hz, 3H), 0.78 (d, J=6.9 Hz, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.34. IR (thin film) 3355, 2965, 1714, 1499, 1366, 1167, 1052, 735 cm.sup.-1. HRMS-ESI (m/z) [M+Na]+ calcd for C.sub.21H.sub.32FNNaO.sub.4, 404.2208; found, 404.2201.

Example 10: Preparation of (2S,3S)-3-(4-fluoro-2-methylphenyl)-4-methylpentan-2-yl (3-hydroxy-4-methoxypicolinoyl)-L-alaninate

Step 1: Preparation of (2S,3S)-3-(4-fluoro-2-methylphenyl)-4-methylpentan-2-yl-L-alaninate Hydrochloride

##STR00052##

[0149] In a small vial, (2S,3S)-3-(4-fluoro-2-methylphenyl)-4-methylpentan-2-yl-(tert-butoxycarbo- nyl)-L-alaninate (35.0 mg, 0.092 mmol) was dissolved in CH.sub.2Cl.sub.2 (2 mL). Hydrogen chloride (4M in dioxane) (0.344 mL, 1.376 mmol) was added in one portion via syringe. The resulting clear, colorless reaction was stirred at room temperature for 3 hr. After 3 hr, TLC indicated complete consumption of the starting material and conversion to a baseline product by TLC. The reaction was concentrated under a stream of N.sub.2 and dried in a vacuum oven to provide (2S,3S)-3-(4-fluoro-2-methylphenyl)-4-methylpentan-2-yl-L-alaninate (26.1 mg, 0.092 mmol, 100% yield) as a clear, colorless oil. ESIMS (m/z) 282.1 [M+H]+. This material was used directly in the next step without further purification.

Step 2: Preparation of (2S,3S)-3-(4-fluoro-2-methylphenyl)-4-methylpentan-2-yl (3-hydroxy-4-methoxypicolinoyl)-L-alaninate

##STR00053##

[0151] To a vial containing (2S,3S)-3-(4-fluoro-2-methylphenyl)-4-methylpentan-2-yl-L-alaninate (26.1 mg, 0.093 mmol) was added 3-hydroxy-4-methoxypicolinic acid (23.53 mg, 0.139 mmol) and ((1H-benzo[d][1,2,3]triazol-1-yl)oxy)tri(pyrrolidin-1-yl)phosphonium hexafluorophosphate(V) (72.4 mg, 0.139 mmol). Dichloromethane (1.86 mL) was added followed by N-ethyl-N-isopropylpropan-2-amine (121 .mu.L, 0.696 mmol) dropwise over 45 seconds. After 10 min, most of the solids solubilized and the resultant pale pink colored reaction was stirred at room temperature overnight. TLC/UPLC indicated consumption of the starting material and formation of a major spot that glowed blue under UV. The reaction was then concentrated under reduced pressure to yield an orange oil. The oil was loaded directly onto a 12 g prepacked silica column in a minimal amount of dichloromethane and purified using Isco silica gel column chromatography (24 column, 30 mL/min, 100% hexanes to 50% acetone:hexanes) to afford (2S,3S)-3-(4-fluoro-2-methylphenyl)-4-methylpentan-2-yl-(3-hydroxy-4-meth- oxypicolinoyl)-L-alaninate (24.4 mg, 0.056 mmol, 60.8% yield) as a clear, colorless oil. .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 12.13 (s, 1H), 8.45 (d, J=8.0 Hz, 1H), 7.99 (d, J=5.2 Hz, 1H), 7.05 (dd, J=8.6, 5.9 Hz, 1H), 6.93-6.77 (m, 3H), 5.38 (dq, J=8.9, 6.3 Hz, 1H), 4.76-4.65 (m, 1H), 3.95 (s, 3H), 3.09 (dd, J=8.9, 6.5 Hz, 1H), 2.29 (s, 3H), 2.11 (h, J=6.8 Hz, 1H), 1.55 (d, J=7.2 Hz, 3H), 1.08 (d, J=6.2 Hz, 3H), 0.86 (d, J=6.8 Hz, 3H), 0.78 (d, J=6.7 Hz, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.30. IR (thin film) 3366, 2961, 1734, 1650, 1529, 1264, 1183, 1049, 955, 801, 735 cm.sup.-1. HRMS-ESI (m/z) [M+H]+ calcd for C.sub.23H.sub.30FN.sub.2O.sub.5, 433.2133; found, 433.2129.

Example 11A: Preparation of (2S,3R)-3-(2,4-dimethylphenyl)-4-methylpentan-2-yl (3-acetoxy-4-methoxypicolinoyl)-L-alaninate

##STR00054##

[0153] To a 20 mL vial charged with (2S,3R)-3-(2,4-dimethylphenyl)-4-methylpentan-2-yl (3-hydroxy-4-methoxypicolinoyl)-L-alaninate (30 mg, 0.070 mmol) dissolved in pyridine (1 mL, 12.36 mmol) was added acetic anhydride (25 .mu.L, 2.65 mmol) at room temperature. After stirring for 45 min, the mixture was concentrated in vacuo and purified via automated silica gel chromatography (0-40% acetone/hexanes as the eluent) to afford (2S,3R)-3-(2,4-dimethylphenyl)-4-methylpentan-2-yl (3-acetoxy-4-methoxypicolinoyl)-L-alaninate (32 mg, 0.061 mmol, 87% yield) as colorless oil. .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 8.56 (s, 1H), 8.35 (d, J=5.4 Hz, 1H), 7.19 (d, J=7.9 Hz, 1H), 7.00 (d, J=5.4 Hz, 1H), 6.94 (d, J=1.9 Hz, 1H), 6.90 (dd, J=7.9, 1.9 Hz, 1H), 5.41 (qd, J=6.3, 4.7 Hz, 1H), 4.77-4.61 (m, 1H), 3.91 (s, 3H), 2.68 (dd, J=9.3, 4.8 Hz, 1H), 2.39 (s, 3H), 2.27 (s, 3H), 2.25 (s, 3H), 2.03 (dp, J=9.2, 6.6 Hz, 1H), 1.38 (d, J=7.2 Hz, 3H), 1.05 (d, J=6.3 Hz, 3H), 0.99 (d, J=6.6 Hz, 3H), 0.69 (d, J=6.8 Hz, 3H). IR (thin film) 3383, 2969, 1772, 1733, 1679, 1200, 1176 cm.sup.-1. HRMS-ESI (m/z) [M+H]+ calcd for C.sub.26H.sub.35N.sub.2O.sub.6, 471.2490; found, 471.2485.

Example 11B: Preparation of (2S,3R)-3-(2,4-dimethylphenyl)-4-methylpentan-2-yl (3-(acetoxymethoxy)-4-methoxypicolinoyl)-L-alaninate

##STR00055##

[0155] To a 20 mL vial charged with in (2S,3R)-3-(2,4-dimethylphenyl)-4-methylpentan-2-yl (3-hydroxy-4-methoxypicolinoyl)-L-alaninate (30 mg, 0.070 mmol) and potassium carbonate (19.35 mg, 0.140 mmol) dissolved in acetone (1.5 mL) was added bromomethyl acetate (0.014 mL, 0.140 mmol) at room temperature. After stirring for 2 hr at 50.degree. C., the mixture was concentrated in vacuo and purified via automated silica gel chromatography (0-40% acetone/hexanes as the eluent) to afford (2S,3R)-3-(2,4-dimethylphenyl)-4-methylpentan-2-yl(3-(acetoxymethoxy)-4-m- ethoxypicolinoyl)-L-alaninate (21 mg, 0.038 mmol, 54% yield) as colorless oil. .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 8.38 (d, J=7.9 Hz, 1H), 8.29 (d, J=5.4 Hz, 1H), 7.20 (d, J=7.9 Hz, 1H), 7.00-6.87 (m, 3H), 5.80-5.69 (m, 2H), 5.42 (qd, J=6.2, 4.7 Hz, 1H), 4.71 (p, J=7.2 Hz, 1H), 3.91 (s, 3H), 2.69 (dd, J=9.2, 4.9 Hz, 1H), 2.27 (s, 3H), 2.25 (s, 3H), 2.10-1.97 (m, 1H), 2.06 (s, 3H), 1.39 (d, J=7.2 Hz, 3H), 1.07 (d, J=6.3 Hz, 3H), 0.99 (d, J=6.6 Hz, 3H), 0.70 (d, J=6.7 Hz, 3H). IR (thin film) 3380, 2969, 1732, 1675, 1502, 1200, 1003, 967, 829 cm.sup.-1. HRMS-ESI (m/z) [M+H]+ calcd for C.sub.27H.sub.37N.sub.2O.sub.7, 501.2595; found, 501.2589.

Example 11C: Preparation of (2S,3S)-3-(3-fluoro-4-methoxyphenyl)-4-methylpentan-2-yl (4-methoxy-3-((3-methoxypropanoyl)oxy)picolinoyl)-L-alaninate

##STR00056##

[0157] To a stirred solution of (2S,3S)-3-(3-fluoro-4-methoxyphenyl)-4-methylpentan-2-yl (3-hydroxy-4-methoxypicolinoyl)-L-alaninate (59.3 mg, 0.132 mmol) and 4-(dimethylamino)pyridine (3.23 mg, 0.026 mmol) dissolved in CH.sub.2Cl.sub.2 (2.0 mL) was added triethylamine (0.037 mL, 0.264 mmol) followed by 3-methoxypropanoyl chloride (0.022 mL, 0.198 mmol). The reaction was allowed to stir at room temperature overnight. The reaction was concentrated under a stream of nitrogen. The residue was loaded directly onto a 12 g prepacked silica column in a minimal amount of dichloromethane and purified using Isco silica gel column chromatography (24 g column, 35 mL/min, 100% hexanes to 50% acetone:hexanes as the eluent) to afford the title compound (58.5 mg, 83% yield) as a pale yellow oil. .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.51 (d, J=7.9 Hz, 1H), 8.34 (d, J=5.4 Hz, 1H), 7.01 (d, J=5.5 Hz, 1H), 6.92-6.75 (m, 3H), 5.34 (dq, J=8.3, 6.2 Hz, 1H), 4.66 (dt, J=8.1, 7.1 Hz, 1H), 3.90 (s, 3H), 3.86 (s, 3H), 3.81 (t, J=6.6 Hz, 2H), 3.40 (s, 3H), 2.99 (t, J=6.6 Hz, 2H), 2.64 (dd, J=8.6, 6.5 Hz, 1H), 2.05 (h, J=6.8 Hz, 1H), 1.49 (d, J=7.2 Hz, 3H), 1.09 (d, J=6.3 Hz, 3H), 0.87 (d, J=6.7 Hz, 3H), 0.75 (d, J=6.7 Hz, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 172.19, 169.42, 162.36, 159.51, 151.94 (d, J=245.0 Hz), 146.73, 146.25 (d, J=10.8 Hz), 141.62, 137.42, 131.84 (d, J=5.6 Hz), 125.47 (d, J=3.6 Hz), 117.15 (d, J=18.2 Hz), 113.05-112.84 (m), 109.77, 72.51, 67.62, 58.76, 56.33, 56.24, 55.74, 48.21, 34.67, 28.35, 21.25, 18.77, 18.63, 17.47. .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -135.76. HRMS-ESI (m/z) [M+H]+ calcd for C.sub.27H.sub.36FN.sub.2O.sub.8, 535.2450; found, 535.2444.

Example 12: Preparation of (1R,2S)-1-cyclopentyl-1-phenylpropan-2-yl(3-acetoxy-4-methoxypyridine-2-c- arbonothioyl)-L-alaninate

Step 1: Preparation of (1R,2S)-1-cyclopentyl-1-phenylpropan-2-yl (3-hydroxy-4-methoxypyridine-2-carbonothioyl)-L-alaninate

##STR00057##

[0159] To a 30 mL vial charged with (1R,2S)-1-cyclopentyl-1-phenylpropan-2-yl (3-hydroxy-4-methoxypicolinoyl)-L-alaninate (99 mg, 0.232 mmol) dissolved in acetonitrile (2.32 mL) was added phosphorous pentasulfide (103 mg, 0.464 mmol) and 1,1,1,3,3,3-hexamethyldisiloxane (248 .mu.L, 1.161 mmol). After stirring for 45 min at 45.degree. C., sat. NaHCO.sub.3 (15 mL) was added followed by aqueous extraction with dichloromethane (3.times.15 mL). The organics were dried over MgSO.sub.4, filtered, and concentrated in vacuo. The crude residue was purified via flash chromatography (0-45% acetone/hexanes as the eluent) to furnish (1R,2S)-1-cyclopentyl-1-phenylpropan-2-yl (3-hydroxy-4-methoxypyridine-2-carbonothioyl)-L-alaninate (72 mg, 0.155 mmol, 66.6% yield) as a yellow oil. .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 12.94 (s, 1H), 10.71 (s, 1H), 8.01 (d, J=15.0 Hz, 1H), 7.22-7.17 (m, 3H), 7.15 (dd, J=6.7, 3.0 Hz, 2H), 6.89 (d, J=5.0 Hz, 1H), 5.39 (qd, J=6.4, 4.0 Hz, 1H), 5.12-5.03 (m, 1H), 3.97 (s, 3H), 2.41 (dd, J=10.4, 4.0 Hz, 1H), 2.25-2.14 (m, 1H), 1.95-1.84 (m, 1H), 1.69-1.59 (m, 1H), 1.56 (d, J=7.2 Hz, 3H), 1.54-1.45 (m, 2H), 1.44-1.28 (m, 2H), 1.19 (dq, J=12.3, 9.1 Hz, 1H), 1.09 (d, J=6.4 Hz, 3H), 0.92 (ddt, J=12.5, 10.0, 8.5 Hz, 1H). IR (thin film) 2951, 2868, 1733, 1581, 1514, 1480, 1454, 1377, 1342, 1274, 1249, 1211, 1131, 1095, 992, 913, 860, 801, 736, 703 cm.sup.-1. HRMS-ESI (m/z) [M+Na]+ calcd for C.sub.24H.sub.30N.sub.2O.sub.4SNa, 465.1818; found, 465.1830.

Step 2: Preparation of (1R,2S)-1-cyclopentyl-1-phenylpropan-2-yl (3-acetoxy-4-methoxypyridine-2-carbonothioyl)-L-alaninate

##STR00058##

[0161] To a solution of (1R,2S)-1-cyclopentyl-1-phenylpropan-2-yl (3-hydroxy-4-methoxypyridine-2-carbonothioyl)-L-alaninate (55 mg, 0.124 mmol) dissolved in pyridine (1 mL, 0.124 mmol) was added acetic anhydride (0.25 mL, 0.124 mmol). After stirring for 1 hr at room temperature, the mixture was concentrated in vacuo and purified via automated column chromatography (0-50% acetone/hexanes as the eluent) to furnish (1R,2S)-1-cyclopentyl-1-phenylpropan-2-yl (3-acetoxy-4-methoxypyridine-2-carbonothioyl)-L-alaninate (34 mg, 0.060 mmol, 48.0% yield) as a brown oil. .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 9.98 (d, J=7.3 Hz, 1H), 8.35 (d, J=5.4 Hz, 1H), 7.25-7.13 (m, 5H), 7.01 (d, J=5.5 Hz, 1H), 5.39 (qd, J=6.3, 4.1 Hz, 1H), 5.16 (p, J=7.2 Hz, 1H), 3.91 (s, 3H), 2.42 (dd, J=10.3, 4.0 Hz, 1H), 2.35 (s, 3H), 2.28-2.19 (m, 1H), 1.93-1.83 (m, 1H), 1.68-1.59 (m, 1H), 1.52 (d, J=7.2 Hz, 3H), 1.50-1.31 (m, 4H), 1.20 (dq, J=12.5, 9.1 Hz, 1H), 1.08 (d, J=6.4 Hz, 3H), 0.97-0.90 (m, 1H). IR (thin film) 2950, 2868, 1770, 1731, 1585, 1496, 1438, 1365, 1311, 1278, 1193, 1175, 1131, 1102, 1040, 1010, 909, 847, 824, 759, 703 cm.sup.-1. HRMS-ESI (m/z) [M+Na]+ calcd for C.sub.26H.sub.32N.sub.2O.sub.5SNa, 507.1924; found, 507.1920.

Example 13: Preparation of 2-(((S)-1-(((2S,3R)-3-(2,4-dimethylphenyl)-4-methylpentan-2-yl)oxy)-1-oxo- propan-2-yl)carbamoyl)-3-hydroxy-4-methoxypyridine 1-oxide

##STR00059##

[0163] To a 25 mL vial charged with (2S,3R)-3-(2,4-dimethylphenyl)-4-methylpentan-2-yl (3-hydroxy-4-methoxypicolinoyl)-L-alaninate (38 mg, 0.089 mmol) dissolved in CH.sub.2Cl.sub.2 (1182 .mu.L) was added 3-chlorobenzoperoxoic acid (mCPBA, 43.7 mg, 0.177 mmol) at room temperature. After stirring overnight, the reaction mixture was concentrated in vacuo and purified via automated silica gel chromatography (0-50% acetone/hexanes as the eluent) to afford 2-(((S)-1-(((2S,3R)-3-(2,4-dimethylphenyl)-4-methylpentan-2-yl)oxy)-1-oxo- propan-2-yl)carbamoyl)-3-hydroxy-4-methoxypyridine 1-oxide (27 mg, 0.055 mmol, 61.6% yield) as colorless oil. .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 14.37 (s, 1H), 12.78 (d, J=7.0 Hz, 1H), 7.88 (d, J=7.1 Hz, 1H), 7.15 (d, J=7.7 Hz, 1H), 6.90 (d, J=8.0 Hz, 2H), 6.77 (d, J=7.2 Hz, 1H), 5.42 (qd, J=6.3, 5.0 Hz, 1H), 4.69-4.61 (m, 1H), 3.96 (s, 3H), 2.69 (dd, J=9.1, 5.0 Hz, 1H), 2.25 (s, 3H), 2.23 (s, 3H), 2.00 (dp, J=8.8, 6.6 Hz, 1H), 1.44 (d, J=7.2 Hz, 3H), 1.08 (d, J=6.3 Hz, 3H), 0.98 (d, J=6.6 Hz, 3H), 0.69 (d, J=6.8 Hz, 3H). IR (thin film) 2964, 1734, 1644, 1571, 1480, 1302, 1216 cm.sup.-1. HRMS-ESI (m/z) [M+H]+ calcd for C.sub.24H.sub.33N.sub.2O.sub.6, 445.2333; found, 445.2370.

Example 14: Preparation of (2S,3R)-3-(2,4-dimethylphenyl)-4-methylpentan-2-yl (S)-2-(8-methoxy-2,4-dioxo-2H-pyrido[2,3-e][1,3]oxazin-3(4H)-yl)propanoat- e

##STR00060##

[0165] To a 20 mL vial charged with (2S,3R)-3-(2,4-dimethylphenyl)-4-methylpentan-2-yl (3-hydroxy-4-methoxypicolinoyl)-L-alaninate (30 mg, 0.070 mmol) and triphosgene (41.5 mg, 0.140 mmol) dissolved in CH.sub.2Cl.sub.2 (0.75 mL) was added pyridine (0.1 mL, 1.236 mmol) at room temperature. After stirring for 45 min at room temperature, the crude LCMS revealed a complete conversion to the desired mass. The reaction mixture was quenched by the addition of a saturated NaHCO.sub.3 solution and was extracted with EtOAc (3.times.10 mL). The combined organic layers were washed with brine (10 mL). The organic solution was dried over Na.sub.2SO.sub.4, filtered and concentrated in vacuo. The residue was purified via automated silica gel chromatography (0-40% acetone/hexanes as the eluent) to afford (2S,3R)-3-(2,4-dimethylphenyl)-4-methylpentan-2-yl(S)-2-(8-methoxy-2,4-di- oxo-2H-pyrido[2,3-e][1,3]oxazin-3(4H)-yl)propanoate (28 mg, 0.059 mmol, 84% yield) as orange oil. .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 8.62 (d, J=5.3 Hz, 1H), 7.15 (d, J=5.4 Hz, 1H), 6.90 (d, J=7.9 Hz, 1H), 6.87-6.83 (m, 1H), 6.32-6.24 (m, 1H), 5.65 (q, J=7.1 Hz, 1H), 5.43 (qd, J=6.4, 3.2 Hz, 1H), 4.05 (s, 3H), 2.53 (dd, J=10.4, 3.2 Hz, 1H), 2.18 (s, 3H), 2.10 (s, 3H), 2.06-1.96 (m, 1H), 1.71 (d, J=7.0 Hz, 3H), 1.04 (d, J=6.5 Hz, 3H), 0.95 (d, J=6.3 Hz, 3H), 0.60 (d, J=6.6 Hz, 3H). IR (thin film) 2958, 1770, 1715, 1371, 1244, 734 cm.sup.-1. HRMS-ESI (m/z) [M+H]+ calcd for C.sub.25H.sub.31N.sub.2O.sub.6, 455.2177; found, 455.2171.

Example A: Evaluation of Fungicidal Activity: Leaf Blotch of Wheat (Zymoseptoria tritici; Bayer Code SEPTTR)

[0166] Technical grades of materials were dissolved in acetone, which were then mixed with nine volumes of water containing 110 ppm Triton X-100. The fungicide solutions were applied onto wheat seedlings using an automated booth sprayer to run-off. All sprayed plants were allowed to air dry prior to further handling. All fungicides were evaluated using the aforementioned method for their activity vs. all target diseases, unless stated otherwise. Wheat leaf blotch and brown rust activity were also evaluated using track spray applications, in which case the fungicides were formulated as EC formulations, containing 0.1% Trycol 5941 in the spray solutions.

[0167] Wheat plants (variety Yuma) were grown from seed in a greenhouse in 50% mineral soil/50% soil-less Metro mix until the first leaf was fully emerged, with 7-10 seedlings per pot. These plants were inoculated with an aqueous spore suspension of Zymoseptoria tritici either prior to or after fungicide treatments. After inoculation the plants were kept in 100% relative humidity (one day in a dark dew chamber followed by two to three days in a lighted dew chamber at 20.degree. C.) to permit spores to germinate and infect the leaf. The plants were then transferred to a greenhouse set at 20.degree. C. for disease to develop. When disease symptoms were fully expressed on the 1.sup.st leaves of untreated plants, infection levels were assessed on a scale of 0 to 100 percent disease severity. Percent disease control was calculated using the ratio of disease severity on treated plants relative to untreated plants.

Example B: Evaluation of Fungicidal Activity: Wheat Brown Rust (Puccinia triticina; Synonym: Puccinia recondita f. Sp. Tritici; Bayer Code PUCCRT)

[0168] Wheat plants (variety Yuma) were grown from seed in a greenhouse in 50% mineral soil/50% soil-less Metro mix until the first leaf was fully emerged, with 7-10 seedlings per pot. These plants were inoculated with an aqueous spore suspension of Puccinia triticina either prior to or after fungicide treatments. After inoculation the plants were kept in a dark dew room at 22.degree. C. with 100% relative humidity overnight to permit spores to germinate and infect the leaf. The plants were then transferred to a greenhouse set at 24.degree. C. for disease to develop. Fungicide formulation, application and disease assessment followed the procedures as described in the Example A.

Example C: Evaluation of Fungicidal Activity: Asian Soybean Rust (Phakopsora pachyrhizi; Bayer Code PHAKPA)

[0169] Technical grades of materials were dissolved in acetone, which were then mixed with nine volumes of water containing 0.011% Tween 20. The fungicide solutions were applied onto soybean seedlings using an automated booth sprayer to run-off. All sprayed plants were allowed to air dry prior to further handling.

[0170] Soybean plants (variety Williams 82) were grown in soil-less Metro mix, with one plant per pot. Two week old seedlings were used for testing. Plants were inoculated either 3 days prior to or 1 day after fungicide treatments. Plants were incubated for 24 h in a dark dew room at 22.degree. C. and 100% relative humidity then transferred to a growth room at 23.degree. C. for disease to develop. Disease severity was assessed on the sprayed leaves.

Example D: Evaluation of Fungicidal Activity: Tomato Early Blight (Alternaria solani; Bayer Code ALTESO)

[0171] Tomato plants (variety Outdoor Girl) were propagated in soil-less Metro mix, with each pot having one plant, and used when 12 to 14 days old. Test plants were inoculated with an aqueous spore suspension of Alternaria solani 24 hr after fungicide treatments. After inoculation the plants were kept in 100% relative humidity (one day in a dark dew chamber followed by two to three days in a lighted dew chamber at 20.degree. C.) to permit spores to germinate and infect the leaf. The plants were then transferred to a growth room at 22.degree. C. for disease to develop. Fungicide formulation, application and disease assessment on the sprayed leaves followed the procedures as described in the Example A.

Example E: Evaluation of Fungicidal Activity: Leaf Spot of Sugar Beets (Cercospora beticola; Bayer Code CERCBE)

[0172] Sugar beet plants (variety HH88) were grown in soil-less Metro mix and trimmed regularly to maintain a uniform plant size prior to test. Plants were inoculated with a spore suspension 24 hr after fungicide treatments. Inoculated plants were kept in a dew chamber at 22.degree. C. for 48 hr then incubated in a greenhouse set at 24.degree. C. under a clear plastic hood with bottom ventilation until disease symptoms were fully expressed. Fungicide formulation, application and disease assessment on the sprayed leaves followed the procedures as described in the Example A.

Example F: Evaluation of Fungicidal Activity: Cucumber Anthracnose (Glomerella lagenarium; Anamorph: Colletotrichum lagenarium; Bayer Code COLLLA)

[0173] Cucumber seedlings (variety Bush Pickle) were propagated in soil-less Metro mix, with each pot having one plant, and used in the test when 12 to 14 days old. Test plants were inoculated with an aqueous spore suspension of Colletotrichum lagenarium 24 hr after fungicide treatments. After inoculation the plants were kept in a dew room at 22.degree. C. with 100% relative humidity for 48 hr to permit spores to germinate and infect the leaf. The plants were then transferred to a growth room set at 22.degree. C. for disease to develop. Fungicide formulation, application and disease assessment on the sprayed leaves followed the procedures as described in the Example A.

Example G: Evaluation of Fungicidal Activity: Wheat Glume Blotch (Parastagonospora nodorum; Bayer Code LEPTNO)

[0174] Wheat plants (variety Yuma) were grown from seed in a greenhouse in 50% mineral soil/50% soil-less Metro mix until the first leaf was fully emerged, with 7-10 seedlings per pot. These plants were inoculated with an aqueous spore suspension of Parastagonospora nodorum 24 hr after fungicide treatments. After inoculation the plants were kept in 100% relative humidity (one day in a dark dew chamber followed by two days in a lighted dew chamber at 20.degree. C.) to permit spores to germinate and infect the leaf. The plants were then transferred to a greenhouse set at 20.degree. C. for disease to develop. Fungicide formulation, application and disease assessment followed the procedures as described in the Example A.

Example H: Evaluation of Fungicidal Activity: Cucumber Downy Mildew (Pseudoperonospora cubensis; Bayer Code PSPECU)

[0175] Cucumber seedlings (variety Bush Pickle) were grown in soil-less Metro mix, with one plant per pot, and used in the test when 12 to 14 days old. Plants were inoculated with a spore suspension 24 hr following fungicide treatments. Test plants were inoculated with an aqueous spore suspension of Pseudoperonospora cubensis 24 hr after fungicide treatments. After inoculation the plants were kept in a dew room at 22.degree. C. with 100% relative humidity for 24 hr to permit spores to germinate and infect the leaf. The plants were then transferred to a greenhouse set at 20.degree. C. until disease was fully expressed. Fungicide formulation, application and disease assessment on the sprayed leaves followed the procedures as described in the Example A.

Example I: Evaluation of Fungicidal Activity: Rice Blast (Magnaporthe grisea; Anamorph: Pyricularia oryzae; Bayer Code PYRIOR)

[0176] Rice seedlings (variety Japonica) were propagated in soil-less Metro mix, with each pot having 8 to 14 plants, and used in the test when 12 to 14 days old. Test plants were inoculated with an aqueous spore suspension of Pyricularia oryzae 24 hr after fungicide treatments. After inoculation, the plants were kept in a dew room at 22.degree. C. with 100% relative humidity for 48 hr to permit spores to germinate and infect the leaf. The plants were then transferred to a greenhouse set at 24.degree. C. for disease to develop. Fungicide formulation, application and disease assessment on the sprayed leaves followed the procedures as described in the Example A.

Example J: Evaluation of Fungicidal Activity: Barley Scald (Rhyncosporium secalis; Bayer Code RHYNSE)

[0177] Barley seedlings (variety Harrington) were propagated in soil-less Metro mix, with each pot having 8 to 12 plants, and used in the test when first leaf was fully emerged. Test plants were inoculated by an aqueous spore suspension of Rhyncosporium secalis 24 hr after fungicide treatments. After inoculation the plants were kept in a dew room at 20.degree. C. with 100% relative humidity for 48 hr. The plants were then transferred to a greenhouse set at 20.degree. C. for disease to develop. Fungicide formulation, application and disease assessment on the sprayed leaves followed the procedures as described in the Example A.

Example K: Evaluation of Fungicidal Activity: Grape Powdery Mildew (Uncinula necator; Bayer Code UNCINE)

[0178] Grape seedlings (variety Carignane) were grown in soil-less Metro mix, with one plant per pot, and used in the test when approximately 1 month old. Plants were inoculated 24 hr after fungicide treatment by shaking spores from infected leaves over test plants. Plants were maintained in a greenhouse set at 20.degree. C. until disease was fully developed. Fungicide formulation, application and disease assessment on sprayed leaves followed the procedures as described in the Example A.

TABLE-US-00001 TABLE 1 Compound Structure, Appearance, and Preparation Method As Prepared Cmpd. According No. Structure To Appearance 1 ##STR00061## Example 2A Example 3B Example 8 Colorless Oil 2 ##STR00062## Example 2A Example 3B Example 8 Colorless Oil 3 ##STR00063## Example 2A Example 3B Example 9 Colorless Oil 4 ##STR00064## Example 1A Example 2B Example 3B Example 8 Colorless Oil 5 ##STR00065## Example 1A Example 2B Example 3B Example 8 Pale Yellow Oil 6 ##STR00066## Example 1B Example 2B Example 3B Example 8 Colorless Oil 7 ##STR00067## Example 2A Example 5 Example 8 Colorless Oil 8 ##STR00068## Example 2A Example 5 Example 8 Colorless Oil 9 ##STR00069## Example 1C; Step 1 Example 2B Example 3B Example 8 Clear, Colorless Oil 10 ##STR00070## Example 1C; Step 1 Example 2B Example 3B Example 8 Clear, Colorless Oil 11 ##STR00071## Example 1C; Step 1 Example 2B Example 3B Example 8 Clear, Colorless Oil 12 ##STR00072## Example 1C; Step 1 Example 2B Example 3B Example 8 Clear, Colorless Oil 13 ##STR00073## Example 1C; Step 1 Example 2B Example 3B Example 8 Clear, Colorless Oil 14 ##STR00074## Example 1C; Step 1 Example 2B Example 3A Example 8 Clear, Colorless Oil 15 ##STR00075## Example 1C; Step 1 Example 2B Example 3B Example 9 Clear, Colorless Oil 16 ##STR00076## Example 1C; Step 1 Example 2B Example 3B Example 9 Clear, Colorless Oil 17 ##STR00077## Example 1C; Step 1 Example 2B Example 4A Example 4C Example 9 Clear, Colorless Oil 18 ##STR00078## Example 1C; Step 1 Example 2B Example 3B Example 9 Clear, Colorless Oil 19 ##STR00079## Example 1C; Step 1 Example 2B Example 3B Example 9 Clear, Colorless Oil 20 ##STR00080## Example 1C; Step 1 Example 2B Example 3A Example 9 Clear, Colorless Oil 21 ##STR00081## Example 1C; Step 1 Example 2B Example 3B Example 8 Clear, Colorless Oil 22 ##STR00082## Example 1C; Step 1 Example 2B Example 3B Example 8 Clear, Colorless Oil 23 ##STR00083## Example 1C; Step 1 Example 2B Example 4A Example 4B Example 8 Clear, Colorless Oil 24 ##STR00084## Example 1D Example 2B Example 3B Example 8 Yellow Oil 25 ##STR00085## Example 1D Example 2B Example 3B Example 8 Colorless Oil 26 ##STR00086## Example 1D Example 2B Example 3B Example 8 Colorless Oil 27 ##STR00087## Example 1D Example 2B Example 3B Example 8 Colorless Oil 28 ##STR00088## Example 1C Example 2B Example 3B Example 8 Clear, Colorless Oil 29 ##STR00089## Example 1C Example 2B Example 3B Example 8 Clear, Colorless Oil 30 ##STR00090## Example 1C Example 2B Example 3B Example 8 Clear, Colorless Oil 31 ##STR00091## Example 1C Example 2B Example 3B Example 8 Clear, Colorless Oil 32 ##STR00092## Example 1C Example 2B Example 3B Example 8 Clear, Colorless Oil 33 ##STR00093## Example 6 Steps 1, 2, 3, 4, 5 Example 8 Colorless Oil 34 ##STR00094## Example 1C Example 2B Example 3A Example 8 Clear, Colorless Oil 35 ##STR00095## Example 1C Example 2B Example 3B Example 7 Example 8 Clear, Colorless Oil 36 ##STR00096## Example 1C Example 2B Example 3B Example 7 Example 8 Clear, Colorless Oil 37 ##STR00097## Example 1C Example 2B Example 3B Example 7 Example 8 Clear, Colorless Oil 38 ##STR00098## Example 1C Example 2B Example 3B Example 7 Example 8 Clear, Colorless Oil 39 ##STR00099## Example 1C Example 2B Example 3A Example 7 Example 8 Clear, Colorless Oil 40 ##STR00100## Example 1C Example 2B Example 4A Example 4C Example 7 Example 8 Clear, Colorless Oil 41 ##STR00101## Example 1D Example 2B Example 3A Example 8 Colorless Oil 42 ##STR00102## Example 6 Steps 1, 2, 6, 7, 4, 5 Example 8 Colorless Oil 43 ##STR00103## Example 6 Steps 1, 2, 6, 7, 4, 5 Example 8 Colorless Oil 44 ##STR00104## Example 6 Steps 1, 2, 6, 7, 4, 5 Example 8 Colorless Oil 45 ##STR00105## Example 6 Steps 1, 2, 6, 7, 4, 5 Example 8 Pale Yellow Oil 46 ##STR00106## Example 6 Steps 1, 2, 6, 7, 4, 5 Example 8 Clear, Colorless Oil 47 ##STR00107## Example 6 Steps 1, 2, 6, 7, 4, 5 Example 8 Clear, Colorless Oil 48 ##STR00108## Example 6 Steps 1, 2, 6, 7, 4, 5 Example 8 Pale Yellow Oil 49 ##STR00109## Example 6 Steps 1, 2, 6, 7, 4, 5 Example 8 Clear, Colorless Oil 50 ##STR00110## Example 6 Steps 1, 2, 6, 7, 4, 5 Example 8 Colorless Oil 51 ##STR00111## Example 6 Steps 1, 2, 6, 7, 4, 5 Example 8 Colorless Oil 52 ##STR00112## Example 10 Step 1 Colorless Oil 53 ##STR00113## Example 10 Step 1 Colorless Oil 54 ##STR00114## Example 10 Step 1 Colorless Oil 55 ##STR00115## Example 10 Step 1 Colorless Oil 56 ##STR00116## Example 10 Step 1 White Semisolid 57 ##STR00117## Example 10 Step 1 Colorless Oil 58 ##STR00118## Example 10 Step 1 Colorless Oil 59 ##STR00119## Example 10 Step 1 Colorless Oil 60 ##STR00120## Example 10 Step 1 Colorless Oil 61 ##STR00121## Example 10 Step 1 Colorless Oil 62 ##STR00122## Example 10 Step 1 Clear, Colorless Oil 63 ##STR00123## Example 10 Step 1 Clear, Colorless Oil 64 ##STR00124## Example 10 Step 1 Pale Yellow Oil 65 ##STR00125## Example 10 Step 1 Clear, Colorless Oil 66 ##STR00126## Example 10 Step 1 Clear, Colorless Oil 67 ##STR00127## Example 10 Step 1 Clear, Colorless Oil 68 ##STR00128## Example 10 Step 1 Pale Yellow Oil 69 ##STR00129## Example 10 Step 1 Clear, Colorless Oil 70 ##STR00130## Example 10 Step 1 Clear, Colorless Oil 71 ##STR00131## Example 10 Step 1 Pale Yellow Oil 72 ##STR00132## Example 10 Step 1 Pale Yellow Oil 73 ##STR00133## Example 10 Step 1 Pale Yellow Oil 74 ##STR00134## Example 10 Step 1 Clear, Colorless Oil 75 ##STR00135## Example 10 Step 1 Clear, Colorless Oil 76 ##STR00136## Example 10 Step 1 Clear, Colorless Oil 77 ##STR00137## Example 10 Step 1 Yellow Oil 78 ##STR00138## Example 10 Step 1 Yellow Oil 79 ##STR00139## Example 10 Step 1 Yellow Oil 80 ##STR00140## Example 10 Step 1 Yellow Oil 81 ##STR00141## Example 10 Step 1 Thick Oil 82 ##STR00142## Example 10 Step 1 Pale Yellow Oil 83 ##STR00143## Example 10 Step 1 Clear, Colorless Oil 84 ##STR00144## Example 10 Step 1 Clear, Colorless Oil 85 ##STR00145## Example 10 Step 1 Clear, Colorless Oil 86 ##STR00146## Example 10 Step 1 Clear, Colorless Oil 87 ##STR00147## Example 10 Step 1 Clear, Colorless Oil 88 ##STR00148## Example 10 Step 1 Clear, Colorless Oil 89 ##STR00149## Example 10 Step 1 White Semisolid 90 ##STR00150## Example 10 Step 1 Off-White Semisolid 91 ##STR00151## Example 10 Step 1 Clear, Colorless Oil 92 ##STR00152## Example 10 Step 1 Clear, Colorless Oil 93 ##STR00153## Example 10 Step 1 Clear, Colorless Oil 94 ##STR00154## Example 10 Step 1 Yellow Oil 95 ##STR00155## Example 10 Step 1 Thick Oil 96 ##STR00156## Example 10 Step 1 Thick Oil 97 ##STR00157## Example 10 Step 1 Thick Oil 98 ##STR00158## Example 10 Step 1 Pale Yellow Oil 99 ##STR00159## Example 10 Step 1 White Semisolid 100 ##STR00160## Example 10 Step 1 Clear, Colorless Oil

101 ##STR00161## Example 10 Step 1 Pale Yellow Oil 102 ##STR00162## Example 10 Step 1 Clear, Colorless Oil 103 ##STR00163## Example 10 Step 1 Yellow Oil 104 ##STR00164## Example 10 Step 1 Yellow Oil 105 ##STR00165## Example 10 Step 2 Colorless Gel 106 ##STR00166## Example 10 Step 2 Colorless Gel 107 ##STR00167## Example 10 Step 2 Colorless Oil 108 ##STR00168## Example 10 Step 2 Colorless Oil 109 ##STR00169## Example 10 Step 2 Clear, Colorless Oil 110 ##STR00170## Example 10 Step 2 Colorless Oil 111 ##STR00171## Example 10 Step 2 Colorless Oil 112 ##STR00172## Example 10 Step 2 Colorless Oil 113 ##STR00173## Example 10 Step 2 Colorless Oil 114 ##STR00174## Example 10 Step 2 Yellow Solid 115 ##STR00175## Example 10 Step 2 Yellow Oil 116 ##STR00176## Example 10 Step 2 Clear, Colorless Oil 117 ##STR00177## Example 10 Step 2 Clear, Colorless Oil 118 ##STR00178## Example 10 Step 2 Clear, Colorless Oil 119 ##STR00179## Example 10 Step 2 Clear, Colorless Oil 120 ##STR00180## Example 10 Step 2 Clear, Colorless Oil 121 ##STR00181## Example 10 Step 2 Clear, Colorless Oil 122 ##STR00182## Example 10 Step 2 Clear, Colorless Oil 123 ##STR00183## Example 10 Step 2 Clear, Colorless Oil 124 ##STR00184## Example 10 Step 2 Clear, Colorless Oil 125 ##STR00185## Example 10 Step 2 Clear, Colorless Oil 126 ##STR00186## Example 10 Step 2 Clear, Colorless Oil 127 ##STR00187## Example 10 Step 2 Clear, Colorless Oil 128 ##STR00188## Example 10 Step 2 Clear, Colorless Oil 129 ##STR00189## Example 10 Step 2 Clear, Colorless Oil 130 ##STR00190## Example 10 Step 2 Clear, Colorless Oil 131 ##STR00191## Example 10 Step 2 Colorless Oil 132 ##STR00192## Example 10 Step 2 Colorless Oil 133 ##STR00193## Example 10 Step 2 White Wax 134 ##STR00194## Example 10 Step 2 White Wax 135 ##STR00195## Example 10 Step 2 Thick Oil 136 ##STR00196## Example 10 Step 2 Bright Yellow Semisolid 137 ##STR00197## Example 10 Step 2 Yellow Oil 138 ##STR00198## Example 10 Step 2 Pale Yellow Oil 139 ##STR00199## Example 10 Step 2 Yellow Oil 140 ##STR00200## Example 10 Step 2 Pale Yellow Oil 141 ##STR00201## Example 10 Step 2 Clear, Colorless Oil 142 ##STR00202## Example 10 Step 2 Clear, Colorless Oil 143 ##STR00203## Example 10 Step 2 Clear, Colorless Oil 144 ##STR00204## Example 10 Step 2 Clear, Colorless Oil 145 ##STR00205## Example 10 Step 2 Clear, Colorless Oil 146 ##STR00206## Example 10 Step 2 Clear, Colorless Oil 147 ##STR00207## Example 10 Step 2 Clear, Colorless Oil 148 ##STR00208## Example 10 Step 2 Clear, Colorless Oil 149 ##STR00209## Example 10 Step 2 Colorless Oil 150 ##STR00210## Example 10 Step 2 Colorless Oil 151 ##STR00211## Example 10 Step 2 Thick Oil 152 ##STR00212## Example 10 Step 2 Thick Oil 153 ##STR00213## Example 10 Step 2 Clear, Colorless Oil 154 ##STR00214## Example 10 Step 2 Clear, Colorless Oil 155 ##STR00215## Example 10 Step 2 Clear, Colorless Oil 156 ##STR00216## Example 10 Step 2 Clear, Colorless Oil 157 ##STR00217## Example 10 Step 2 Clear, Colorless Oil 158 ##STR00218## Example 10 Step 2 Colorless Oil 159 ##STR00219## Example 10 Step 2 Colorless Oil 160 ##STR00220## Example 11A Colorless Oil 161 ##STR00221## Example 11A Colorless Oil 162 ##STR00222## Example 11B Colorless Oil 163 ##STR00223## Example 11B Colorless Oil 164 ##STR00224## Example 11B Colorless Oil 165 ##STR00225## Example 11A Colorless Oil 166 ##STR00226## Example 11A Colorless Oil 167 ##STR00227## Example 11B Colorless Oil 168 ##STR00228## Example 11A Clear, Colorless Oil 169 ##STR00229## Example 11A Colorless Oil 170 ##STR00230## Example 11A Colorless Oil 171 ##STR00231## Example 11B Colorless Oil 172 ##STR00232## Example 11A Colorless Oil 173 ##STR00233## Example 11A Colorless Oil 174 ##STR00234## Example 11B Colorless Oil 175 ##STR00235## Example 11B Colorless Oil 176 ##STR00236## Example 12 Orange Wax 177 ##STR00237## Example 12 Brown Oil 178 ##STR00238## Example 11A Clear, Colorless Oil 179 ##STR00239## Example 11A Clear, Colorless Oil 180 ##STR00240## Example 11A Clear, Colorless Oil 181 ##STR00241## Example 11A Pale Yellow Oil 182 ##STR00242## Example 11A Clear, Colorless Oil 183 ##STR00243## Example 11A Clear, Colorless Oil 184 ##STR00244## Example 11A Clear, Colorless Oil 185 ##STR00245## Example 11A Clear, Colorless Oil 186 ##STR00246## Example 11A Clear, Colorless Oil 187 ##STR00247## Example 11A Clear, Colorless Oil 188 ##STR00248## Example 11A Clear, Colorless Oil 189 ##STR00249## Example 11A Clear, Colorless Oil 190 ##STR00250## Example 11A Clear, Colorless Oil 191 ##STR00251## Example 11A Clear, Colorless Oil 192 ##STR00252## Example 11A Clear, Colorless Oil 193 ##STR00253## Example 11B Clear, Colorless Oil 194 ##STR00254## Example 11B Clear, Colorless Oil 195 ##STR00255## Example 11B Clear, Colorless Oil 196 ##STR00256## Example 11B Clear, Colorless Oil 197 ##STR00257## Example 11B Clear, Colorless Oil 198 ##STR00258## Example 11B White Semisolid 199 ##STR00259## Example 11B Clear, Colorless Oil 200 ##STR00260## Example 11A Colorless Oil 201 ##STR00261## Example 11A Colorless Oil 202 ##STR00262## Example 11A Colorless Oil 203 ##STR00263## Example 11A Colorless Oil 204 ##STR00264## Example 11B Colorless Oil 205 ##STR00265## Example 11B Colorless Oil 206 ##STR00266## Example 11B Colorless Oil 207 ##STR00267## Example 11B Colorless Oil 208 ##STR00268## Example 14 Orange Oil 209 ##STR00269## Example 14 Orange Oil 210 ##STR00270## Example 14 Orange Foam 211 ##STR00271## Example 13 Colorless Oil 212 ##STR00272## Example 13 Colorless Oil 213 ##STR00273## Example 13 Colorless Oil 214 ##STR00274## Example 11A White Foam 215 ##STR00275## Example 11B Pale Yellow Oil 216 ##STR00276## Example 11C Clear, Colorless Oil 217 ##STR00277## Example 14 Pale Yellow Oil 218 ##STR00278## Example 13 Clear, Colorless Oil 219 ##STR00279## Example 12 Yellow Oil 220 ##STR00280## Example 11C Pale Yellow Oil 221 ##STR00281## Example 11A Pale Yellow Oil 222 ##STR00282## Example 11A Yellow Oil 223 ##STR00283## Example 11A Clear, Colorless Oil 224 ##STR00284## Example 11A Clear, Colorless Oil 225 ##STR00285## Example 11A Clear, Colorless Oil 226 ##STR00286## Example 11A Clear, Colorless Oil

227 ##STR00287## Example 11A Clear, Colorless Oil 228 ##STR00288## Example 11A Clear, Colorless Oil 229 ##STR00289## Example 11A Clear, Colorless Oil 230 ##STR00290## Example 11A Clear, Colorless Oil 231 ##STR00291## Example 11A Clear, Colorless Oil 232 ##STR00292## Example 11A Clear, Colorless Oil 233 ##STR00293## Example 11B Clear, Colorless Oil 234 ##STR00294## Example 11B Clear, Colorless Oil 235 ##STR00295## Example 11B Clear, Colorless Oil 236 ##STR00296## Example 11B Clear, Colorless Oil 237 ##STR00297## Example 11B Clear, Colorless Oil 238 ##STR00298## Example 11C Clear, Colorless Oil 239 ##STR00299## Example 11C Clear, Colorless Oil 240 ##STR00300## Example 11B Yellow Oil 241 ##STR00301## Example 11A Colorless Oil 242 ##STR00302## Example 11A Thick Oil 243 ##STR00303## Example 11A White Foam 244 ##STR00304## Example 11A Thick Oil 245 ##STR00305## Example 11C Pale Yellow Oil 246 ##STR00306## Example 11C Clear, Colorless Oil 247 ##STR00307## Example 11C Pale Yellow Oil 248 ##STR00308## Example 11C Pale Yellow Oil 249 ##STR00309## Example 11C Clear, Colorless Oil 250 ##STR00310## Example 11A Clear, Colorless Oil 251 ##STR00311## Example 11A Clear, Colorless Oil 252 ##STR00312## Example 11A Clear, Colorless Oil 253 ##STR00313## Example 11A Clear, Colorless Oil 254 ##STR00314## Example 11A Clear, Colorless Oil 255 ##STR00315## Example 11B Clear, Colorless Oil 256 ##STR00316## Example 11B Clear, Colorless Oil 257 ##STR00317## Example 11B Clear, Colorless Oil 258 ##STR00318## Example 11B Clear, Colorless Oil 259 ##STR00319## Example 11B Clear, Colorless Oil 260 ##STR00320## Example 11B Clear, Colorless Oil 261 ##STR00321## Example 11A Colorless Oil 262 ##STR00322## Example 11A Colorless Oil 263 ##STR00323## Example 11B Yellow Oil 264 ##STR00324## Example 11B Yellow Oil 265 ##STR00325## Example 10 Step 1 Clear, Colorless Oil 266 ##STR00326## Example 10 Step 1 Clear, Colorless Oil 267 ##STR00327## Example 10 Step 1 Clear, Colorless Oil 268 ##STR00328## Example 10 Step 1 White Semisolid 269 ##STR00329## Example 10 Step 1 White Solid 270 ##STR00330## Example 10 Step 1 White Solid 271 ##STR00331## Example 10 Step 1 White Solid 272 ##STR00332## Example 10 Step 1 White Solid 273 ##STR00333## Example 10 Step 1 White Solid 274 ##STR00334## Example 10 Step 1 White Solid 275 ##STR00335## Example 10 Step 1 White Solid 276 ##STR00336## Example 10 Step 1 Thick Oil 277 ##STR00337## Example 10 Step 1 Thick Oil 278 ##STR00338## Example 10 Step 1 Thick Oil 279 ##STR00339## Example 10 Step 1 Thick Oil 280 ##STR00340## Example 10 Step 1 Thick Oil 281 ##STR00341## Example 10 Step 1 Thick Oil 282 ##STR00342## Example 10 Step 1 Yellow Oil 283 ##STR00343## Example 10 Step 1 Colorless Semi-Solid 284 ##STR00344## Example 10 Step 1 Yellow Oil 285 ##STR00345## Example 10 Step 1 Yellow Oil 286 ##STR00346## Example 10 Step 1 Colorless Oil 287 ##STR00347## Example 10 Step 1 Residue 288 ##STR00348## Example 1D Example 2B Example 4A Example 4B Example 7 Example 8 Clear, Colorless Oil 289 ##STR00349## Example 1D Example 2B Example 4A Example 4B Example 7 Example 8 Clear, Colorless Oil 290 ##STR00350## Example 1D Example 2B Example 4A Example 4B Example 7 Example 8 White Semisolid 291 ##STR00351## Example 1D Example 2B Example 4A Example 4B Example 7 Example 8 Clear, Colorless Oil 292 ##STR00352## Example 6A Example 7 Example 8 Colorless Oil 293 ##STR00353## Example 6A Example 7 Example 8 Colorless Oil 294 ##STR00354## Example 6A Example 7 Example 8 Colorless Oil 295 ##STR00355## Example 6A Example 7 Example 8 Colorless Oil 296 ##STR00356## Example 6A Example 7 Example 8 Colorless Oil 297 ##STR00357## Example 6A Example 7 Example 8 Colorless Oil 298 ##STR00358## Example 6A Example 7 Example 8 Colorless Oil 299 ##STR00359## Example 6A Example 7 Example 8 Oil 300 ##STR00360## Example 6A Example 7 Example 8 Oil 301 ##STR00361## Example 6A Example 7 Example 8 Oil 302 ##STR00362## Example 6A Example 7 Example 8 Colorless Oil 303 ##STR00363## Example 6A Example 7 Example 8 Oil 304 ##STR00364## Example 6A Example 7 Example 8 Oil 305 ##STR00365## Example 6 Steps 2A, 6, 7, 4, 5 Example 7 Example 8 Colorless Oil 306 ##STR00366## Example 6 Steps 2A, 6, 7, 4, 5 Example 7 Example 8 Colorless Oil 307 ##STR00367## Example 6 Steps 2A, 6, 7, 4, 5 Example 7 Example 8 White Wax 308 ##STR00368## Example 6 Steps 2A, 6, 7, 4, 5 Example 7 Example 8 Colorless Oil 309 ##STR00369## Example 6 Steps 1, 2, 6, 7, 4, 5 Example 8 Colorless Oil 310 ##STR00370## Example 1E Example 2B Example 3B Example 7 Example 8 Residue 311 ##STR00371## Example 1E Example 2B Example 3B Example 7 Example 8 Residue 312 ##STR00372## Example 6A Example 7 Example 8 Residue 313 ##STR00373## Example 6A Example 7 Example 8 Residue 314 ##STR00374## Example 6A Example 7 Example 8 Residue 315 ##STR00375## Example 6A Example 7 Example 8 Residue 316 ##STR00376## Example 6A Example 7 Example 8 Residue 317 ##STR00377## Example 10 Step 2 Clear, Colorless Oil 318 ##STR00378## Example 10 Step 2 Clear, Colorless Oil 319 ##STR00379## Example 10 Step 2 Clear, Colorless Oil 320 ##STR00380## Example 10 Step 2 Clear, Colorless Oil 321 ##STR00381## Example 10 Step 2 Colorless Oil 322 ##STR00382## Example 10 Step 2 Colorless Oil 323 ##STR00383## Example 10 Step 2 Colorless Oil 324 ##STR00384## Example 10 Step 2 Colorless Oil 325 ##STR00385## Example 10 Step 2 Colorless Oil 326 ##STR00386## Example 10 Step 2 Colorless Oil 327 ##STR00387## Example 10 Step 2 Off-White Wax 328 ##STR00388## Example 10 Step 2 White Foam 329 ##STR00389## Example 10 Step 2 White Foam 330 ##STR00390## Example 10 Step 2 Thick Oil 331 ##STR00391## Example 10 Step 2 Thick Oil 332 ##STR00392## Example 10 Step 2 Thick Oil 333 ##STR00393## Example 10 Step 2 Thick Oil 334 ##STR00394## Example 10 Step 2 Yellow Oil 335 ##STR00395## Example 10 Step 2 Yellow Oil 336 ##STR00396## Example 10 Step 2 Yellow Oil 337 ##STR00397## Example 10 Step 2 Colorless Oil 338 ##STR00398## Example 10 Step 2 Colorless Oil 339 ##STR00399## Example 10 Step 2 Residue 340 ##STR00400## Example 10 Step 2 Residue 341 ##STR00401## Example 10 Step 2 Residue 342 ##STR00402## Example 10 Step 2 Residue 343 ##STR00403## Example 10 Step 2 Residue 344 ##STR00404## Example 10 Step 2 Residue 345 ##STR00405## Example 10 Step 2 Residue 346 ##STR00406## Example 11A Clear, Colorless Oil

347 ##STR00407## Example 11A Clear, Colorless Oil 348 ##STR00408## Example 11A Clear, Colorless Oil 349 ##STR00409## Example 11A Clear, Colorless Oil 350 ##STR00410## Example 11C Clear, Colorless Oil 351 ##STR00411## Example 11C Clear, Colorless Oil 352 ##STR00412## Example 11C Clear, Colorless Oil 353 ##STR00413## Example 11C Clear, Colorless Oil 354 ##STR00414## Example 11C Clear, Colorless Oil 355 ##STR00415## Example 11C Pale Yellow Oil 356 ##STR00416## Example 11C Clear, Colorless Oil 357 ##STR00417## Example 11C Clear, Colorless Oil 358 ##STR00418## Example 11A White Foam 359 ##STR00419## Example 11A White Foam 360 ##STR00420## Example 11A Colorless Oil 361 ##STR00421## Example 11A Colorless Oil 362 ##STR00422## Example 11A Colorless Oil 363 ##STR00423## Example 11A Colorless Oil 364 ##STR00424## Example 11A Colorless Oil 365 ##STR00425## Example 11A White Foam 366 ##STR00426## Example 11A White Foam 367 ##STR00427## Example 11A White Foam 368 ##STR00428## Example 11A White Foam 369 ##STR00429## Example 11A Thick Oil 370 ##STR00430## Example 11A Thick Oil 371 ##STR00431## Example 11C White Foam 372 ##STR00432## Example 11C Thick Oil 373 ##STR00433## Example 11C Colorless Oil 374 ##STR00434## Example 11C Thick Oil 375 ##STR00435## Example 11C Colorless Oil 376 ##STR00436## Example 11A Colorless Oil 377 ##STR00437## Example 11A Colorless Oil 378 ##STR00438## Example 11B Yellow Oil 379 ##STR00439## Example 11B Yellow Oil 380 ##STR00440## Example 11A Glassy White Solid 381 ##STR00441## Example 11A Colorless Oil 382 ##STR00442## Example 11B Yellow Oil 383 ##STR00443## Example 11A Colorless Oil 384 ##STR00444## Example 11A Residue 385 ##STR00445## Example 11A Residue 386 ##STR00446## Example 11C Residue 387 ##STR00447## Example 11C Residue 388 ##STR00448## Example 11A Residue 389 ##STR00449## Example 11A Residue 390 ##STR00450## Example 11A Residue 391 ##STR00451## Example 11A Residue 392 ##STR00452## Example 11A Residue *Cmpd. No.--Compound Number

TABLE-US-00002 TABLE 2 Analytical Data Melting Cmpd. Point No. (.degree. C.) IR (cm.sup.-1) MASS SPEC NMR 1 ESIMS m/z 350.5 .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. ([M + H].sup.+) 7.31-7.12 (m, 5H), 5.50-5.38 (m, 1H), 5.02 (d, J = 7.8 Hz, 1H), 4.29-4.17 (m, 1H), 2.36 (dd, J = 8.4, 5.6 Hz, 1H), 2.13-1.96 (m, 1H), 1.44 (s, 9H), 1.14 (d, J = 7.2 Hz, 3H), 1.11 (d, J = 6.3 Hz, 3H), 0.94 (d, J = 6.6 Hz, 3H), 0.72 (d, J = 6.7 Hz, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 172.83, 157.91, 139.85, 129.62, 127.92, 126.50, 79.70, 71.92, 58.00, 49.41, 29.18, 28.33, 21.29, 20.19, 18.97, 18.54. 2 ESIMS m/z 376.6 .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. ([M + H].sup.+) 7.38-7.14 (m, 5H), 5.33 (qd, J = 6.4, 3.9 Hz, 1H), 5.07 (d, J = 8.0 Hz, 1H), 4.40-4.23 (m, 1H), 2.41 (dd, J = 10.3, 4.0 Hz, 1H), 2.29-2.13 (m, 1H), 1.92-1.79 (m, 1H), 1.70-1.61 (m, 1H), 1.59-1.48 (m, 2H), 1.45 (s, 9H), 1.45-1.32 (m, 2H), 1.31 (d, J = 7.2 Hz, 3H), 1.27-1.13 (m, 1H), 1.06 (d, J = 6.3 Hz, 3H), 1.04-0.88 (m, 1H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 172.79, 155.00, 140.76, 129.49, 127.96, 126.49, 79.75, 73.15, 56.65, 49.52, 42.13, 31.61, 31.47, 28.34, 25.12, 24.53, 18.81. 3 ESIMS m/z 350.5 .sup.1H NMR (300 MHz, CDCl.sub.3) .delta. ([M + H].sup.+) 7.36-7.20 (m, 3H), 7.16-7.03 (m, 2H), 5.40 (dq, J = 8.8, 6.2 Hz, 1H), 5.09 (d, J = 8.0 Hz, 1H), 4.39-4.15 (m, 1H), 2.70 (dd, J = 8.9, 6.3 Hz, 1H), 2.20-2.01 (m, 1H), 1.45 (s, 9H), 1.39 (d, J = 7.2 Hz, 3H), 1.08 (d, J = 6.2 Hz, 3H), 0.86 (d, J = 6.8 Hz, 3H), 0.76 (d, J = 6.8 Hz, 3H). 4 ESIMS m/z 365 ([M + H].sup.+) .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.18-7.02 (m, 4H), 5.36-5.22 (m, 1H), 5.07 (s, 1H), 4.36-4.19 (m, 1H), 2.33 (s, 3H), 1.97 (dd, J = 10.0, 7.1 Hz, 1H), 1.45 (s, 9H), 1.36 (d, J = 7.2 Hz, 3H), 1.15 (d, J = 6.3 Hz, 3H), 1.12-1.00 (m, 1H), 0.73-0.57 (m, 1H), 0.47-0.27 (m, 2H), -0.01--0.15 (m, 1H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 172.79, 155.03, 138.55, 136.15, 128.94, 128.28, 75.73, 68.48, 55.27, 49.50, 28.35, 21.01, 18.87, 18.19, 13.04, 6.90, 2.83. 5 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. film) 3358, calcd for C.sub.21H.sub.33NNaO.sub.4, 7.13-7.05 (m, 2H), 7.00-6.94 (m, 2H), 2976, 386.2302; found, 386.2306 5.38 (dq, J = 8.9, 6.3 Hz, 1H), 5.13 (d, J = 7.9 Hz, 1715, 1H), 4.28 (p, J = 7.5 Hz, 1H), 1514, 2.66 (dd, J = 8.9, 6.2 Hz, 1H), 2.33 (s, 1366, 3H), 2.09 (h, J = 6.8 Hz, 1H), 1.45 (s, 1167, 1052 cm.sup.-1 9H), 1.39 (d, J = 7.2 Hz, 3H), 1.07 (d, J = 6.3 Hz, 3H), 0.85 (d, J = 6.8 Hz, 3H), 0.76 (d, J = 6.7 Hz, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 172.82, 155.03, 136.11, 135.47, 129.67, 128.65, 79.66, 72.59, 56.29, 49.56, 28.36, 28.16, 21.39, 21.00, 18.81, 18.42, 17.98. 6 ESIMS m/z 366 ([M + H].sup.+) .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.22-7.12 (m, 2H), 7.03-6.94 (m, 2H), 5.32-5.20 (m, 1H), 5.04 (d, J = 8.0 Hz, 1H), 4.40-4.22 (m, 1H), 2.01 (dd, J = 10.1, 6.7 Hz, 1H), 1.45 (s, 9H), 1.34 (d, J = 7.2 Hz, 3H), 1.16 (d, J = 6.4 Hz, 3H), 1.13-1.07 (m, 1H), 0.76-0.63 (m, 1H), 0.46-0.31 (m, 2H), -0.03--0.10 (m, 1H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -116.47. 7 ESIMS m/z 378 ([M + H].sup.+) .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.32-7.02 (m, 5H), 5.48-5.34 (m, 1H), 5.10 (bs, 1H), 4.35-4.21 (m, 1H), 2.94 (dd, J = 8.6, 6.3 Hz, 1H), 1.64-1.55 (m, 1H), 1.45 (s, 9H), 1.66-1.54 (m, 2H), 1.30-1.12 (m, 2H), 1.39 (d, J = 7.2 Hz, 3H), 1.08 (d, J = 6.3 Hz, 3H), 0.96 (t, J = 7.4 Hz, 3H), 0.78 (t, J = 7.3 Hz, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 172.72, 154.99, 138.99, 129.76, 127.94, 126.61, 72.12, 51.91, 49.49, 41.54, 28.35, 22.30, 19.03, 17.95, 11.68, 11.13. 8 ESIMS m/z 376 ([M + H].sup.+) .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.36-7.04 (m, 5H), 5.34-5.26 (m, 1H), 5.14-4.97 (m, 1H), 4.28 (m, 1H), 2.76 (dd, J = 9.9, 6.1 Hz, 1H), 2.35-2.10 (m, 2H), 1.96-1.83 (m, 2H), 1.45 (s, 9H), 1.36 (d, J = 7.2 Hz, 3H), 1.33-0.98 m, 5H), 1.10 (d, J = 6.5 Hz, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 172.62, 140.75, 140.10, 129.62, 127.90, 126.55, 74.02, 55.12, 41.77, 31.46, 31.26, 28.35, 25.30, 24.45, 18.88, 16.30. 9 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.27 (q, film) 3358, calcd for C.sub.21H.sub.32FNNaO.sub.4, J = 3.3 Hz, 1H), 6.91-6.82 (m, 2H), 2975, 404.2208; found, 404.2202 5.45-5.33 (m, 1H), 5.03 (d, J = 7.9 Hz, 1712, 1H), 4.35-4.18 (m, 1H), 2.69 (dd, 1498, J = 9.2, 5.0 Hz, 1H), 2.28 (s, 3H), 1165, 862 cm.sup.-1 2.02 (dp, J = 9.1, 6.7 Hz, 1H), 1.44 (s, 9H), 1.34-1.17 (m, 4H), 1.06 (d, J = 6.3 Hz, 3H), 0.98 (d, J = 6.5 Hz, 3H), 0.70 (d, J = 6.7 Hz, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 172.75, 160.98 (d, J = 243.9 Hz), 155.01, 139.40 (d, J = 7.3 Hz), 134.70 (d, J = 2.9 Hz), 129.37 (d, J = 8.1 Hz), 116.46 (d, J = 20.4 Hz), 112.69 (d, J = 20.5 Hz), 79.81, 72.22, 50.66, 49.49, 30.41, 28.34, 20.99, 20.73 (d, J = 1.5 Hz), 20.44, 18.65, 18.40. .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.64. 10 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.31 (dd, film) 3358, calcd for C.sub.23H.sub.36FNNaO.sub.4, J = 8.4, 6.1 Hz, 1H), 6.86 (dd, J = 9.2, 2966, 432.2521; found, 432.2515 7.4 Hz, 2H), 5.36 (qd, J = 6.3, 4.5 Hz, 1715, 1H), 5.05 (d, J = 8.0 Hz, 1H), 1498, 1167 cm.sup.-1 4.39-4.21 (m, 1H), 2.91 (dd, J = 10.0, 4.3 Hz, 1H), 2.30 (s, 3H), 1.74 (ddq, J = 14.1, 10.2, 4.6 Hz, 1H), 1.52 (ddt, J = 14.5, 7.4, 4.0 Hz, 1H), 1.44 (d, J = 2.1 Hz, 9H), 1.42-1.34 (m, 2H), 1.34-1.28 (m, 2H), 1.26-1.03 (m, 2H), 1.01 (d, J = 6.2 Hz, 3H), 0.88 (t, J = 7.4 Hz, 3H), 0.76 (q, J = 7.7 Hz, 1H), 0.70 (t, J = 7.4 Hz, 2H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 172.82, 160.98 (d, J = 244.1 Hz), 154.98, 139.43 (d, J = 7.3 Hz), 134.74 (d, J = 3.3 Hz), 129.78 (d, J = 8.0 Hz), 116.45 (d, J = 20.6 Hz), 112.75 (d, J = 20.7 Hz), 79.82, 71.95, 49.49, 45.70, 41.63, 28.36, 21.76, 21.12, 20.61, 18.83, 18.39, 10.77, 9.56. .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.60. 11 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.30 (dd, film) 3357, calcd for C.sub.23H.sub.34FNNaO.sub.4, J = 8.5, 6.1 Hz, 1H), 6.86 (t, J = 8.2 Hz, 2954, 430.2364; found, 430.2361 2H), 5.31 (td, J = 6.5, 4.4 Hz, 1H), 1711, 5.06 (d, J = 7.8 Hz, 1H), 4.39-4.20 (m, 1497, 1H), 2.80 (dd, J = 10.3, 4.3 Hz, 1H), 1164, 860, 2.30 (s, 3H), 2.26-2.10 (m, 1H), 732 cm.sup.-1 1.88 (dtd, J = 11.0, 6.9, 3.3 Hz, 1H), 1.74-1.48 (m, 2H), 1.48-1.33 (m, 11H), 1.33-1.13 (m, 4H), 1.11-1.00 (m, 4H), 0.96-0.81 (m, 1H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 172.69, 160.94 (d, J = 243.9 Hz), 155.01, 138.84 (d, J = 7.2 Hz), 135.28 (d, J = 3.1 Hz), 129.66 (d, J = 8.1 Hz), 116.43 (d, J = 20.2 Hz), 112.70 (d, J = 20.4 Hz), 79.82, 73.45, 49.55, 49.41, 42.93, 31.61, 31.35, 28.35, 25.13, 24.42, 20.61, 18.72, 18.22. .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.66. 12 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. film) 3357, calcd for C.sub.24H.sub.36FNNaO.sub.4, 7.32-7.26 (m, 1H), 6.90-6.81 (m, 2H), 2928, 444.2521; found, 444.2514 5.47-5.35 (m, 1H), 5.07 (d, J = 7.9 Hz, 1709, 1H), 4.31 (q, J = 7.4 Hz, 1H), 2.76 (dd, 1497, J = 9.2, 4.9 Hz, 1H), 2.27 (s, 3H), 1206, 860, 1.84 (dt, J = 12.6, 3.2 Hz, 1H), 731 cm.sup.-1 1.79-1.53 (m, 3H), 1.45 (s, 9H), 1.41-1.30 (m, 1H), 1.30-1.25 (m, 3H), 1.25-0.87 (m, 8H), 0.80 (qt, J = 12.1, 6.1 Hz, 1H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 172.81, 160.94 (d, J = 243.9 Hz), 154.99, 139.46 (d, J = 7.2 Hz), 134.70 (d, J = 3.2 Hz), 129.43 (d, J = 7.9 Hz), 116.39 (d, J = 20.5 Hz), 112.73 (d, J = 20.5 Hz), 79.78, 71.54, 49.67, 49.44, 40.28, 31.31, 30.73, 28.38, 26.45, 26.40, 26.34, 20.73, 18.79, 18.29. .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.65. 13 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.27 (d, film) 3357, calcd for C.sub.22H.sub.34FNNaO.sub.4, J = 6.3 Hz, 1H), 6.91-6.80 (m, 2H), 2971, 418.2364; found, 418.2360 5.50-5.32 (m, 1H), 5.03 (s, 1H), 1712, 4.27 (dt, J = 13.6, 7.2 Hz, 1H), 2.79 (ddd, J = 43.4, 1498, 9.2, 5.1 Hz, 1H), 2.28 (d, J = 1.8 Hz, 1164, 860 cm.sup.-1 3H), 1.81 (dtdd, J = 19.1, 9.5, 6.3, 3.1 Hz, 1H), 1.68-1.50 (m, 1H), 1.44 (d, J = 3.1 Hz, 9H), 1.36-1.13 (m, 3H), 1.13-0.57 (m, 10H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.61, -117.68. 14 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.09 (dd, film) 3355, calcd for C.sub.22H.sub.32FNNaO.sub.4, J = 8.3, 6.0 Hz, 1H), 6.82 (t, J = 8.4 Hz, 2976, 416.2208; found, 416.2203 2H), 5.11 (t, J = 6.4 Hz, 1H), 4.95 (d, J = 8.0 Hz, 1713 1H), 4.17 (t, J = 7.5 Hz, 1H), 1498, 1166 cm.sup.-1 3.02 (dd, J = 10.4, 6.7 Hz, 1H), 2.65 (q, J = 8.6, 7.8 Hz, 1H), 2.35 (s, 3H), 2.15 (dp, J = 7.4, 5.1, 4.1 Hz, 1H), 1.92-1.75 (m, 2H), 1.75-1.55 (m, 2H), 1.49-1.32 (m, 10H), 1.17 (d, J = 6.3 Hz, 3H), 1.06 (d, J = 7.2 Hz, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.57. 15 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.09 (dd, film) 3356, calcd for C.sub.23H.sub.34FNNaO.sub.4, J = 9.5, 5.9 Hz, 1H), 6.91-6.82 (m, 2954, 430.2364; found, 430.2360 2H), 5.26 (p, J = 6.5 Hz, 1H), 5.03 (s, 1711, 1H), 4.35-4.19 (m, 1H), 3.10 (t, J = 8.3 Hz, 1497, 1H), 2.30 (s, 3H), 1163, 2.21-2.06 (m, 1H), 1.85 (dtd, J = 11.2, 7.3, 3.5 Hz, 1056, 860, 1H), 1.72-1.46 (m, 2H), 1.44 (s, 732 cm.sup.-1 9H), 1.42-1.14 (m, 6H), 1.08 (d, J = 6.4 Hz, 3H), 1.03 (dd, J = 9.1, 6.4 Hz, 1H), 0.91 (dtt, J = 15.2, 7.8, 4.4 Hz, 1H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.51. 16 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.05 (dd, film) 2928, calcd for C.sub.24H.sub.36FNNaO.sub.4, J = 8.3, 5.9 Hz, 1H), 6.91-6.81 (m, 1714, 444.2521; found, 444.2516 2H), 5.36 (dq, J = 9.2, 6.3 Hz, 1H), 1497, 5.08 (d, J = 7.8 Hz, 1H), 4.31 (d, J = 9.1 Hz, 1450, 1H), 3.11 (dd, J = 9.2, 6.0 Hz, 1H), 1366, 2.31 (s, 3H), 1.82-1.50 (m, 6H), 1.45 (s, 1166, 9H), 1.40 (d, J = 7.1 Hz, 3H), 1029, 861, 1.35-1.06 (m, 2H), 1.02 (d, J = 6.3 Hz, 3H), 733 cm.sup.-1 1.00-0.77 (m, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.40. 17 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (400 MHz,

CDCl.sub.3) .delta. 7.05 (dd, film) 3355, calcd for C.sub.21H.sub.32FNNaO.sub.4, J = 8.5, 6.0 Hz, 1H), 6.87 (ddt, J = 11.6, 2965, 404.2208; found, 404.2201 8.3, 4.1 Hz, 2H), 5.33 (dq, J = 9.1, 6.2 Hz, 1714, 1H), 5.05 (d, J = 8.1 Hz, 1H), 1499, 4.28 (d, J = 7.6 Hz, 1H), 3.08 (dd, J = 9.2, 1366, 6.2 Hz, 1H), 2.32 (s, 3H), 1167, 2.18-2.06 (m, 1H), 1.45 (s, 9H), 1.39 (d, J = 7.2 Hz, 1052, 735 cm.sup.-1 3H), 1.03 (d, J = 6.2 Hz, 3H), 0.85 (d, J = 6.8 Hz, 3H), 0.78 (d, J = 6.9 Hz, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.34. 18 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. film) 2963, calcd for C.sub.23H.sub.36FNNaO.sub.4, 7.34 (dd, J = 9.7, 6.0 Hz, 1H), 6.86 (ddd, J = 8.3, 1714, 432.2521; found, 432.2516 5.8, 2.9 Hz, 2H), 5.38 (dq, J = 8.1, 1497, 6.3 Hz, 1H), 5.05 (d, J = 8.2 Hz, 1H), 1453, 4.27 (qd, J = 6.4, 3.6 Hz, 1H), 2.74 (dd, 1367, J = 10.2, 3.6 Hz, 1H), 2.28 (s, 3H), 1166, 1.88 (ddq, J = 10.1, 6.2, 4.0, 3.2 Hz, 1H), 1055, 860 cm.sup.-1 1.69-1.48 (m, 1H), 1.44 (s, 9H), 1.36 (d, J = 7.2 Hz, 1H), 1.35-1.11 (m, 2H), 1.10-0.83 (m, 6H), 0.74 (dt, J = 25.4, 7.3 Hz, 6H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.41, -118.02. 19 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.33 (dd, film) 3442, calcd for C.sub.22H.sub.34FNNaO.sub.4, J = 9.5, 6.0 Hz, 1H), 6.86 (ddt, J = 12.5, 2965, 418.2364; found, 418.2360 8.4, 3.6 Hz, 2H), 5.36 (ddq, J = 15.7, 1713, 9.5, 6.2 Hz, 1H), 5.08 (s, 1H), 4.28 (p, J = 6.3 Hz, 1497, 1H), 2.28 (d, J = 3.9 Hz, 3H), 1453, 2.04-1.57 (m, 1H), 1.45 (d, J = 1.9 Hz, 1367, 9H), 1.42-1.11 (m, 2H), 1165, 1.09-0.99 (m, 3H), 0.99-0.83 (m, 6H), 1055, 954, 0.83-0.74 (m, 3H), 0.68 (d, J = 6.8 Hz, 860 cm.sup.-1 1H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.94, -118.00. 20 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.01 (dd, film) 3356, calcd for C.sub.22H.sub.32FNNaO.sub.4, J = 8.4, 5.9 Hz, 1H), 6.85 (ddt, J = 11.3, 2977, 416.2208; found, 416.2202 8.3, 4.1 Hz, 2H), 5.08 (dd, J = 14.2, 7.6 Hz, 1708, 2H), 4.36-4.05 (m, 1H), 1498, 3.23-3.03 (m, 1H), 2.70 (tt, J = 19.6, 9.3 Hz, 1163, 909 1H), 2.35 (s, 3H), 2.19-2.04 (m, 2H), 731 cm.sup.-1 1.94-1.72 (m, 2H), 1.72-1.54 (m, 1H), 1.44 (s, 9H), 1.37 (d, J = 7.1 Hz, 4H), 1.05 (d, J = 6.3 Hz, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.31. 21 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.33 (dd, film) 3355, calcd for C.sub.23H.sub.34FNNaO.sub.4, J = 8.4, 6.1 Hz, 1H), 6.86 (tt, J = 9.8, 2954, 430.2364; found, 430.2360 2.8 Hz, 2H), 5.30 (qd, J = 6.1, 3.3 Hz, 1711, 1H), 5.05 (d, J = 7.7 Hz, 1H), 1497, 4.42-4.22 (m, 1H), 2.77 (dd, J = 10.8, 3.4 Hz, 1163, 1H), 2.30 (s, 3H), 2.28-2.10 (m, 1066, 2H), 1.93 (dtd, J = 11.5, 7.3, 3.4 Hz, 1019, 860, 1H), 1.75-1.46 (m, 2H), 733 cm.sup.-1 1.46-1.42 (m, 10H), 1.42-1.16 (m, 5H), 1.02 (d, J = 6.4 Hz, 3H), 0.86 (tdd, J = 12.0, 8.6, 6.0 Hz, 1H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 172.72, 160.92 (d, J = 243.9 Hz), 155.10, 138.76 (d, J = 7.3 Hz), 135.17 (d, J = 3.3 Hz), 129.94 (d, J = 7.8 Hz), 116.33 (d, J = 20.5 Hz), 112.67 (d, J = 20.6 Hz), 79.77, 73.09, 49.53, 42.66, 31.71, 28.31, 25.19, 24.50, 20.59, 18.55, 17.80. .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.74. 22 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.33 (dd, film) 3357, calcd for C.sub.24H.sub.36FNNaO.sub.4, J = 8.6, 6.1 Hz, 1H), 6.86 (ddt, J = 9.8, 2928, 444.2521; found, 444.2515 7.1, 4.0 Hz, 2H), 5.47-5.36 (m, 1H), 1711, 5.10-4.94 (m, 1H), 4.37-4.21 (m, 1497, 1H), 2.72 (dd, J = 9.9, 4.0 Hz, 1H), 1165, 860, 2.27 (s, 3H), 1.93 (d, J = 12.7 Hz, 1H), 733 cm.sup.-1 1.80-1.48 (m, 4H), 1.44 (s, 10H), 1.29 (dd, J = 18.3, 7.7 Hz, 4H), 1.16-0.87 (m, 6H), 0.87-0.68 (m, 1H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 172.73, 160.93 (d, J = 244.0 Hz), 155.06, 139.41 (d, J = 7.3 Hz), 134.65 (d, J = 3.3 Hz), 129.67 (d, J = 7.8 Hz), 116.33 (d, J = 20.6 Hz), 112.74 (d, J = 20.5 Hz), 79.80, 71.03, 49.68, 39.93, 31.35, 28.35, 26.51, 26.37, 26.28, 20.74, 18.54, 17.99. .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.76. 23 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.32 (dd, film) 3356, calcd for C.sub.21H.sub.32FNNaO.sub.4, J = 8.4, 6.1 Hz, 1H), 6.92-6.82 (m, 2975, 404.2208; found, 404.2202 2H), 5.40 (qd, J = 6.3, 3.9 Hz, 1H), 1712, 5.00 (d, J = 7.8 Hz, 1H), 4.41-4.18 (m, 1498, 1H), 2.63 (dd, J = 9.5, 4.3 Hz, 1H), 1366, 2.28 (s, 3H), 2.03 (dp, J = 9.7, 6.4 Hz, 1H), 1165, 1.44 (d, J = 3.7 Hz, 9H), 1063, 862, 1.41-1.12 (m, 3H), 1.10-0.95 (m, 5H), 735 cm.sup.-1 0.92-0.74 (m, 1H), 0.67 (d, J = 6.7 Hz, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.72. 24 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. film) 3355, calcd for C.sub.22H.sub.35NO.sub.4Na, 7.21-6.94 (m, 3H), 5.44-5.34 (m, 1H), 2973, 400.2458; found, 400.2452 5.06 (d, J = 7.8 Hz, 1H), 4.33-4.23 (m, 2871, 1H), 2.68 (dd, J = 9.2, 4.9 Hz, 1H), 1713, 2.28 (s, 3H), 2.25 (s, 3H), 2.03 (dp, J = 9.0, 1366, 6.6 Hz, 1H), 1.44 (s, 9H), 1.25 (d, J = 7.3 Hz, 1163, 733 cm.sup.-1 3H), 1.05 (d, J = 6.3 Hz, 3H), 0.98 (d, J = 6.6 Hz, 3H), 0.70 (d, J = 6.7 Hz, 3H). 25 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. film) 3366, calcd for C.sub.24H.sub.37NO.sub.4Na, 7.24-6.91 (m, 3H), 5.30 (dq, J = 6.5, 3.4, 2.2 Hz, 2953, 426.2615; found, 426.2608 1H), 5.08 (d, J = 8.2 Hz, 1H), 1712, 4.34-4.25 (m, 1H), 2.79 (dd, J = 10.3, 4.1 Hz, 1161, 731 cm.sup.-1 1H), 2.29 (s, 3H), 2.27 (s, 3H), 2.25-2.14 (m, 1H), 1.97-1.80 (m, 1H), 1.70-1.61 (m, 1H), 1.58-1.35 (m, 12H), 1.34-1.17 (m, 5H), 1.07 (d, J = 6.3 Hz, 3H), 0.93-0.87 (m, 1H). 26 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 7.21 (d, film) 3360, calcd for C.sub.25H.sub.39NO.sub.4Na, J = 7.9 Hz, 1H), 6.98-6.94 (m, 2H), 2924, 440.2771; found, 440.2765 5.48-5.30 (m, 1H), 5.08 (d, J = 7.9 Hz, 1712, 1H), 4.38-4.23 (m, 1H), 2.75 (dd, J = 9.3, 1162, 732 cm.sup.-1 4.8 Hz, 1H), 2.28 (s, 3H), 2.24 (s, 3H), 1.90-1.83 (m, 1H) 1.79-1.53 (m, 3H), 1.45 (s, 9H), 1.42-1.05 (m, 8H), 1.03 (d, J = 6.2 Hz, 3H), 1.01-0.73 (m, 2H). 27 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. film) 3358, calcd for C.sub.23H.sub.37NO.sub.4Na, 7.23-6.90 (m, 3H), 5.40 (dd, J = 7.7, 4.7 Hz, 2970, 414.2615; found, 414.2610 1H), 5.06 (t, J = 9.1 Hz, 1H), 2931, 4.35-4.21 (m, 1H), 2.87-2.70 (m, 1H), 1713, 2.30-2.24 (m, 6H), 1.92-1.75 (m, 1H), 1163, 733 cm.sup.-1 1.64-1.53 (m, 1H), 1.44 (d, J = 4.3 Hz, 9H), 1.35-1.14 (m, 3H), 1.15-0.62 (m, 10H). 28 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.21 (dd, film) 3358, calcd for C.sub.21H.sub.32FNNaO.sub.5, J = 8.5, 6.9 Hz, 1H), 6.69-6.53 (m, 2973, 420.2157; found, 420.2149 2H), 5.39 (p, J = 5.9 Hz, 1H), 5.05 (d, J = 7.8 Hz, 1711, 1H), 4.33-4.17 (m, 1H), 1501, 1163 cm.sup.-1 3.78 (s, 3H), 3.06 (dd, J = 9.4, 5.0 Hz, 1H), 1.97 (dp, J = 9.2, 6.6 Hz, 1H), 1.44 (s, 9H), 1.27-1.20 (m, 3H), 1.05 (d, J = 6.2 Hz, 3H), 0.95 (d, J = 6.6 Hz, 3H), 0.68 (d, J = 6.7 Hz, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -114.15. 29 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.24 (dd, film) 3358, calcd for C.sub.23H.sub.36FNNaO.sub.5, J = 8.6, 6.9 Hz, 1H), 6.68-6.50 (m, 2965, 448.2470; found, 448.2464 2H), 5.44-5.30 (m, 1H), 5.05 (d, J = 8.1 Hz, 1714, 1H), 4.37-4.18 (m, 1H), 1501, 1165 cm.sup.-1 3.78 (s, 3H), 3.31 (dd, J = 9.7, 4.7 Hz, 1H), 1.76-1.56 (m, 2H), 1.44 (s, 9H), 1.41-1.17 (m, 5H), 1.02 (d, J = 6.2 Hz, 3H), 0.96 (ddd, J = 11.8, 9.1, 6.1 Hz, 1H), 0.88 (t, J = 7.4 Hz, 3H), 0.69 (t, J = 7.4 Hz, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 172.81, 162.06 (d, J = 244.1 Hz), 159.15 (d, J = 9.2 Hz), 154.95, 130.14 (d, J = 9.1 Hz), 124.35 (d, J = 3.5 Hz), 106.70 (d, J = 20.5 Hz), 98.44 (d, J = 25.3 Hz), 79.73, 77.21, 72.04, 55.59, 49.46, 40.99, 28.34, 21.70, 21.48, 18.84, 18.42, 10.26, 10.03. .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -114.14. 30 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.23 (t, J = 7.8 Hz, film) 3356, calcd for C.sub.24H.sub.36FNNaO.sub.5, 1H), 6.69-6.48 (m, 2H), 2929, 460.2470; found, 460.2466 5.47-5.33 (m, 1H), 5.07 (d, J = 8.2 Hz, 1714, 1H), 4.35-4.21 (m, 1H), 3.77 (s, 1502, 1165 cm.sup.-1 3H), 3.13 (s, 1H), 1.87-1.53 (m, 6H), 1.44 (s, 9H), 1.39-1.16 (m, 4H), 1.16-0.85 (m, 6H), 0.78 (qd, J = 12.2, 3.2 Hz, 1H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -114.17. 31 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. film) 3358, calcd for C.sub.23H.sub.34FNNaO.sub.5, 7.29-7.22 (m, 1H), 6.68-6.55 (m, 2H), 2954, 446.2313; found, 446.2309 5.38-5.24 (m, 1H), 5.08 (d, J = 7.9 Hz, 1713, 1H), 4.38-4.21 (m, 1H), 3.78 (s, 3H), 1502, 1165 cm.sup.-1 3.12 (d, J = 10.7 Hz, 1H), 2.16 (qd, J = 10.0, 7.8, 2.9 Hz, 1H), 1.85 (ddt, J = 14.5, 11.1, 5.0 Hz, 1H), 1.74-1.59 (m, 1H), 1.52 (dtd, J = 15.4, 8.4, 3.7 Hz, 1H), 1.44 (d, J = 2.3 Hz, 9H), 1.43-1.14 (m, 6H), 1.03 (d, J = 6.3 Hz, 3H), 1.00-0.81 (m, 2H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -114.20. 32 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. film) 3358, calcd for C.sub.22H.sub.34FNNaO.sub.5, 7.21 (ddd, J = 14.6, 8.6, 6.9 Hz, 1H), 2968, 434.2313; found, 434.2306 6.61 (dddd, J = 15.1, 10.8, 4.4, 2.5 Hz, 2H), 1711, 5.47-5.33 (m, 1H), 5.05 (dd, J = 16.0, 1501, 1163 cm.sup.-1 7.7 Hz, 1H), 4.25 (dt, J = 23.5, 7.3 Hz, 1H), 3.78 (d, J = 1.3 Hz, 3H), 3.31-3.08 (m, 1H), 1.78 (ttd, J = 7.9, 6.3, 5.9, 3.5 Hz, 1H), 1.55-1.35 (m, 10H), 1.34-1.18 (m, 2H), 1.10 (td, J = 15.7, 14.1, 6.9 Hz, 3H), 1.04-0.81 (m, 5H), 0.77-0.61 (m, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -114.11, -114.21. 33 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.06 (dd, film) 3352, calcd for C.sub.20H.sub.30FNO.sub.4Na, J = 8.7, 5.6 Hz, 2H), 7.02-6.92 (m, 2964, 390.2051; found, 390.2044 2H), 5.36 (dq, J = 8.7, 6.3 Hz, 1H), 2932, 5.05 (s, 1H), 4.37-4.19 (m, 1H), 2.69 (dd, J = 8.7, 1712, 6.4 Hz, 1H), 2.08 (h, J = 6.7 Hz, 1605, 1H), 1.45 (s, 8H), 1.38 (d, J = 7.2 Hz, 1509, 3H), 1.06 (d, J = 6.2 Hz, 3H), 0.86 (d, J = 6.8 Hz, 1452, 3H), 0.74 (d, J = 6.8 Hz, 3H). 1366, .sup.13C NMR (126 MHz, CDCl.sub.3) .delta. 172.79, 1224, 161.75 (d, J = 244.8 Hz), 155.03, 1160, 134.29, 131.03 (d, J = 7.6 Hz), 1052, 835 cm.sup.-1 114.82 (d, J = 21.0 Hz), 79.79, 72.32, 55.88, 49.50, 28.34, 28.18, 21.30, 18.81, 18.41, 17.74. 34 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.07 (dd, film) 3358, calcd for C.sub.22H.sub.32FNNaO.sub.5, J = 8.3, 6.8 Hz, 1H), 6.63-6.53 (m, 2976, 432.2157; found, 432.2159 2H), 5.19 (q, J = 6.2 Hz, 1H), 5.00 (d, J = 7.8 Hz, 1710, 1H), 4.18 (d, J = 7.4 Hz, 1H),

1501, 3.79 (s, 3H), 3.24 (s, 1H), 2.64 (h, J = 8.6 Hz, 1276, 1H), 2.11 (ddt, J = 11.6, 6.9, 4.3 Hz, 1164, 1H), 1.88-1.55 (m, 4H), 1035, 954, 1.51-1.35 (m, 10H), 1.16 (d, J = 7.4 Hz, 3H), 833 cm.sup.-1 1.11 (d, J = 6.4 Hz, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -114.07. 35 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.00 (dd, film) 3358, calcd for C.sub.24H.sub.36FNNaO.sub.5, J = 8.3, 6.8 Hz, 1H), 6.60 (ddt, J = 10.7, 2928, 460.2470; found, 460.2470 7.4, 4.1 Hz, 2H), 5.41 (s, 1H), 5.10 (d, J = 8.0 Hz, 1712, 1H), 4.37-4.17 (m, 1H), 1502, 3.76 (s, 3H), 3.36 (s, 1H), 1450, 1.76-1.48 (m, 5H), 1.45 (s, 9H), 1.38 (d, J = 7.1 Hz, 1163, 3H), 1.32-1.16 (m, 2H), 1033, 955, 1.16-0.92 (m, 5H), 0.92-0.72 (m, 2H). 834 cm.sup.-1 .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -113.94. 36 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.05 (t, J = 7.7 Hz, film) 3358, calcd for C.sub.32H.sub.34FNNaO.sub.5, 1H), 6.67-6.53 (m, 2H), 2954, 446.2313; found, 446.2313 5.29 (s, 1H), 5.07 (s, 1H), 4.23 (d, J = 7.9 Hz, 1710, 1H), 3.76 (s, 3H), 3.49 (d, J = 67.4 Hz, 1502, 1H), 2.11 (d, J = 53.5 Hz, 1H), 1450, 1.84 (dtd, J = 10.9, 7.1, 3.4 Hz, 1H), 1366, 1.70-1.58 (m, 1H), 1.58-1.37 (m, 1164, 12H), 1.34 (d, J = 7.1 Hz, 3H), 1033, 953, 1.30-1.18 (m, 2H), 1.09 (d, J = 6.4 Hz, 3H), 834, 732 cm.sup.-1 0.99-0.83 (m, 1H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -114.07. 37 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.04 (dd, film) 3359, calcd for C.sub.23H.sub.36FNNaO.sub.5, J = 8.3, 6.8 Hz, 1H), 6.60 (ddt, J = 11.0, 2965, 448.2470; found, 448.2469 7.6, 2.5 Hz, 2H), 5.40 (dt, J = 12.5, 6.3 Hz, 1713, 1H), 5.20-5.02 (m, 1H), 4.27 (s, 1501, 1H), 3.77 (s, 2H), 3.57 (d, J = 10.1 Hz, 1165, 1H), 1.55 (dt, J = 9.8, 6.7 Hz, 1H), 1054, 1.50-1.42 (m, 10H), 1.42-1.30 (m, 4H), 1035, 955, 1.29-1.09 (m, 2H), 1.06 (d, J = 6.3 Hz, 834 cm.sup.-1 3H), 0.94 (t, J = 7.4 Hz, 3H), 0.91-0.78 (m, 1H), 0.75 (t, J = 7.2 Hz, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -113.91. 38 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.02 (t, J = 7.6 Hz, film) 3358, calcd for C.sub.22H.sub.34FNNaO.sub.5, 1H), 6.66-6.56 (m, 2H), 2966, 434.2313; found, 434.2312 5.40 (tt, J = 10.1, 5.5 Hz, 1H), 5.11 (s, 1711, 1H), 4.29 (dd, J = 15.4, 7.9 Hz, 1H), 1600, 3.77 (d, J = 2.3 Hz, 3H), 3.42 (d, J = 27.2 Hz, 1502, 1H), 1.80 (ddt, J = 8.9, 6.8, 4.4 Hz, 1452, 1H), 1.45 (d, J = 2.2 Hz, 9H), 1366, 1.36 (ddd, J = 14.4, 12.6, 6.9 Hz, 4H), 1164, 1.05 (dd, J = 8.1, 6.2 Hz, 3H), 1053, 0.97-0.82 (m, 4H), 0.76 (dd, J = 11.5, 7.0 Hz, 1035, 954, 3H). 834 cm.sup.-1 .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -113.85, -113.92. 39 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. film) 3359, calcd for C.sub.22H.sub.32FNNaO.sub.5, 7.00-6.93 (m, 1H), 6.58 (ddd, J = 10.0, 6.6, 2976, 432.2157; found, 432.2147 2.0 Hz, 2H), 5.21-4.97 (m, 2H), 1709, 4.24 (d, J = 7.9 Hz, 1H), 3.79 (s, 3H), 1501, 3.31 (s, 1H), 2.76 (h, J = 8.5 Hz, 1H), 1164, 2.12 (dddd, J = 22.7, 20.7, 11.3, 6.7 Hz, 1H), 1035, 954, 1.97-1.74 (m, 2H), 1.74-1.57 (m, 834, 732 cm.sup.-1 2H), 1.50-1.37 (m, 10H), 1.34 (d, J = 7.1 Hz, 3H), 1.06 (d, J = 6.4 Hz, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -113.90. 40 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.01 (dd, film) 3359, calcd for C.sub.21H.sub.32FNNaO.sub.5, J = 8.2, 6.7 Hz, 1H), 6.66-6.57 (m, 2964, 420.2157; found, 420.2154 2H), 5.38 (t, J = 7.4 Hz, 1H), 5.09 (d, J = 7.7 Hz, 1710, 1H), 4.38-4.20 (m, 1H), 1502, 3.77 (s, 3H), 3.32 (s, 1H), 1164, 2.14-2.01 (m, 1H), 1.45 (s, 9H), 1.37 (d, J = 7.2 Hz, 1050, 3H), 1.05 (d, J = 6.2 Hz, 3H), 1034, 954, 0.84 (d, J = 6.8 Hz, 3H), 0.73 (d, J = 6.7 Hz, 834, 732 cm.sup.-1 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -113.87. 41 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. film) 3358, calcd for C.sub.23H.sub.35NO.sub.4Na, 7.09-6.87 (m, 3H), 5.21-5.07 (m, 1H), 2975, 412.2458; found, 412.2463 4.98 (d, J = 7.9 Hz, 1H), 4.29-4.07 (m, 1H), 2935, 3.02 (dd, J = 10.5, 6.3 Hz, 1H), 1713, 2.68 (hept, J = 8.0, 7.1 Hz, 1H), 2.32 (s, 3H), 1164, 1021 cm.sup.-1 2.26 (s, 3H), 2.19-2.08 (m, 1H), 1.88-1.62 (m, 4H), 1.43 (s, 9H), 1.32-1.22 (m, 1H), 1.16 (d, J = 6.4 Hz, 3H), 1.07 (d, J = 7.1 Hz, 3H). 42 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.27 (d, film) 3365, calcd for C.sub.20H.sub.30ClNO.sub.4, J = 9.9 Hz, 2H), 7.03 (d, J = 8.5 Hz, 2969, 409.1763; found, 409.1764 2H), 5.42-5.31 (m, 1H), 2932, 5.13-4.95 (m, 1H), 4.27 (t, 1H), 2.68 (dd, J = 8.6, 2875, 6.5 Hz, 1H), 2.16-1.98 (m, 1H), 1714, 1.45 (s, 9H), 1.38 (d, J = 7.2 Hz, 3H), 1492, 1.07 (d, J = 6.3 Hz, 3H), 0.86 (d, J = 6.8 Hz, 1366, 3H), 0.74 (d, J = 6.8 Hz, 3H). 1166, 1053 cm.sup.-1 .sup.13C NMR (126 MHz, CDCl.sub.3) .delta. 172.76, 137.14, 132.52, 131.02, 128.15, 77.21, 72.15, 56.07, 49.49, 28.35, 28.15, 25.29, 21.27, 18.81, 18.47, 17.70, 14.13. 43 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.09 (t, J = 8.0 Hz, film) 3353, calcd for C.sub.21H.sub.32FNO.sub.4, 1H), 6.80-6.71 (m, 2H), 2969, 406.2268; found, 406.2269 5.40-5.25 (m, 1H), 5.06 (s, 1H), 2931, 4.33-4.22 (m, 1H), 2.65 (dd, J = 8.7, 6.5 Hz, 1714, 1H), 2.25 (d, J = 1.8 Hz, 3H), 1506, 2.13-1.98 (m, 1H), 1.45 (s, 9H), 1.38 (d, J = 7.2 Hz, 1366, 3H), 1.08 (d, J = 6.3 Hz, 3H), 1163, 1052 cm.sup.-1 0.86 (d, J = 6.8 Hz, 3H), 0.76 (d, J = 6.8 Hz, 3H). .sup.13C NMR (126 MHz, CDCl.sub.3) .delta. 172.79, 161.92, 159.98, 138.35, 138.30, 130.82, 130.78, 125.20, 125.17, 123.01, 122.88, 116.22, 116.04, 79.77, 77.21, 72.28, 56.12, 49.50, 34.67, 31.59, 28.34, 28.19, 25.28, 21.29, 18.81, 18.51, 17.74, 14.21, 14.18, 14.13. 44 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.09 (dt, film) 3351, calcd for C.sub.20H.sub.29F.sub.2NO.sub.4, J = 10.1, 8.3 Hz, 1H), 6.92 (ddd, J = 11.7, 2976, 408.1957; found, 408.1956 7.6, 2.2 Hz, 1H), 6.86-6.76 (m, 1709, 1H), 5.31 (dt, J = 8.5, 6.3 Hz, 1H), 1515, 5.03 (s, 1H), 4.27 (s, 1H), 2.72-2.62 (m, 1280, 1H), 2.13-1.96 (m, 1H), 1.45 (s, 9H), 1163, 1.37 (d, J = 7.2 Hz, 3H), 1.08 (d, J = 6.3 Hz, 1053, 771 cm.sup.-1 3H), 0.88 (d, J = 6.8 Hz, 3H), 0.75 (d, J = 6.8 Hz, 3H). .sup.13C NMR (126 MHz, CDCl.sub.3) .delta. 172.72, 125.58, 118.35, 118.21, 116.77, 116.63, 79.84, 77.21, 71.98, 55.92, 49.48, 28.33, 28.24, 21.20, 18.75, 18.57, 17.51. 45 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. film) 2965, calcd for C.sub.21H.sub.32FNNaO.sub.4, 6.96-6.84 (m, 3H), 5.35 (dq, J = 8.8, 6.2 Hz, 1714, 404.2208; found, 404.2208 1H), 5.11 (d, J = 7.8 Hz, 1H), 4.28 (p, J = 7.5 Hz, 1503, 1H), 2.65 (dd, J = 8.9, 6.3 Hz, 1366, 1H), 2.26 (d, J = 1.9 Hz, 3H), 1211, 2.13-2.03 (m, 1H), 1.45 (s, 9H), 1.39 (d, J = 7.2 Hz, 1164, 1052 cm.sup.-1 3H), 1.07 (d, J = 6.3 Hz, 3H), 0.85 (d, J = 6.8 Hz, 3H), 0.75 (d, J = 6.8 Hz, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 172.82, 160.30 (d, J = 243.6 Hz), 155.04, 134.03 (d, J = 3.9 Hz), 132.62 (d, J = 4.9 Hz), 128.31 (d, J = 7.7 Hz), 124.13 (d, J = 17.1 Hz), 114.42 (d, J = 22.0 Hz), 79.75, 72.46, 55.89, 49.56, 28.36, 28.19, 21.34, 18.76, 18.46, 17.87, 14.64 (d, J = 3.5 Hz). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -120.77. 46 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.03 (t, J = 8.5 Hz, film) 3369, calcd for C.sub.21H.sub.32FNNaO.sub.5, 1H), 6.67 (ddd, J = 8.6, 2.6, 2965, 420.2157; found, 420.2158 0.8 Hz, 1H), 6.60 (dd, J = 12.0, 2.6 Hz, 1714, 1H), 5.44-5.34 (m, 1H), 5.13 (d, J = 8.0 Hz, 1508, 1H), 4.28 (dd, J = 11.1, 4.2 Hz, 1366, 1H), 3.79 (s, 3H), 3.08 (dd, J = 8.5, 6.8 Hz, 1293, 1H), 2.15-2.05 (m, 1H), 1.45 (s, 1165, 9H), 1.38 (d, J = 7.2 Hz, 3H), 1.09 (d, J = 6.3 Hz, 1053, 1032 cm.sup.-1 3H), 0.90 (dd, J = 6.7, 1.0 Hz, 3H), 0.76 (d, J = 6.7 Hz, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 172.80, 162.10 (d, J = 244.2 Hz), 159.37 (d, J = 11.4 Hz), 155.06, 130.68 (d, J = 6.6 Hz), 117.55 (d, J = 15.5 Hz), 109.59 (d, J = 3.0 Hz), 101.42 (d, J = 27.9 Hz), 79.66, 72.25, 55.44, 49.55, 47.97, 28.35, 21.11, 18.84, 18.60, 17.55. .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -113.07. 47 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. film) 3369, calcd for C.sub.21H.sub.32FNNaO.sub.5, 6.93-6.77 (m, 3H), 5.32 (dq, J = 8.6, 6.2 Hz, 2965, 420.2157; found, 420.2160 1H), 5.17-5.04 (m, 1H), 4.28 (dd, J = 11.1, 1712, 4.1 Hz, 1H), 3.88 (s, 3H), 1515, 2.63 (dd, J = 8.7, 6.4 Hz, 1H), 1273, 2.13-2.00 (m, 1H), 1.45 (s, 9H), 1.38 (d, J = 7.2 Hz, 1221, 3H), 1.08 (d, J = 6.3 Hz, 3H), 1164, 0.86 (d, J = 6.8 Hz, 3H), 0.76 (d, J = 6.8 Hz, 1052, 1028 cm.sup.-1 3H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 172.78, 155.04, 151.97 (d, J = 245.2 Hz), 146.32 (d, J = 10.6 Hz), 131.77 (d, J = 5.7 Hz), 125.40 (d, J = 3.6 Hz), 117.21 (d, J = 18.3 Hz), 112.98 (d, J = 2.1 Hz), 79.75, 72.30, 56.25, 55.81, 49.53, 28.35, 28.25, 21.30, 18.75, 18.51, 17.72. .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -135.65. 48 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 6.94 (d, film) 3355, calcd for C.sub.22H.sub.35NNaO.sub.5, J = 7.7 Hz, 1H), 6.72 (dd, J = 7.6, 1.5 Hz, 2963, 416.2407; found, 416.2410 1H), 6.68 (d, J = 1.6 Hz, 1H), 1714, 5.40 (t, J = 7.7 Hz, 1H), 5.14 (d, J = 7.4 Hz, 1506, 1H), 4.35-4.20 (m, 1H), 3.76 (s, 3H), 1454, 3.32 (s, 1H), 2.33 (s, 3H), 2.08 (dq, J = 12.5, 1366, 6.3, 5.8 Hz, 1H), 1.45 (s, 9H), 1256, 1.38 (d, J = 7.2 Hz, 3H), 1.05 (d, J = 6.2 Hz, 1163, 3H), 0.84 (d, J = 6.8 Hz, 3H), 1050 cm.sup.-1 0.74 (d, J = 6.8 Hz, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 172.75, 158.09, 155.01, 137.18, 129.51, 124.60, 120.74, 111.75, 79.60, 73.28, 55.34, 53.89, 49.67, 29.30, 28.76, 28.37, 21.44, 21.12, 18.79, 18.12. 49 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. film) 3364, calcd for C.sub.22H.sub.35NNaO.sub.5, 7.03-6.95 (m, 1H), 6.71 (d, J = 7.9 Hz, 2H), 2961, 416.2407; found, 416.2404 5.33 (dq, J = 9.4, 6.2 Hz, 1H), 5.12 (d, J = 7.9 Hz, 1712, 1H), 4.38-4.20 (m, 1H), 1502, 3.78 (s, 3H), 3.05 (dd, J = 9.4, 5.9 Hz, 1453, 1H), 2.31 (s, 3H), 2.12 (dq, J = 13.4, 1366, 6.7 Hz, 1H), 1.45 (s, 9H), 1.40 (d, J = 7.2 Hz, 1250, 3H), 1.03 (d, J = 6.2 Hz, 3H), 1162, 0.84 (d, J = 6.8 Hz, 3H), 0.79 (d, J = 6.9 Hz, 1048, 732 cm.sup.-1 3H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 172.89, 157.60, 155.00, 138.86, 129.96, 128.86, 115.89, 110.91, 79.71, 73.89, 55.04, 49.60, 49.24, 29.58, 28.35, 21.08, 20.98, 18.72, 18.64, 18.33. 50 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. film) 3363, calcd for C.sub.22H.sub.35NO.sub.6Na, 7.04-6.82 (m, 1H), 6.50-6.30 (m, 2H),

2962, 432.2357; found, 432.2347 5.50-5.28 (m, 1H), 5.11 (d, J = 7.4 Hz, 1H), 1712, 4.36-4.17 (m, 1H), 3.80 (s, 3H), 1505, 3.76 (s, 3H), 3.44-3.00 (m, 1H), 2.06 (h, J = 6.7 Hz, 1207, 1H), 1.45 (s, 9H), 1.38 (d, J = 7.1 Hz, 1157, 3H), 1.05 (d, J = 6.2 Hz, 3H), 1045, 732 cm.sup.-1 0.83 (d, J = 6.8 Hz, 3H), 0.73 (d, J = 6.8 Hz, 3H). 51 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. film) 3359, calcd for C.sub.21H.sub.33NO.sub.5Na, 7.25-7.13 (m, 1H), 7.07 (dd, J = 7.6, 1.8 Hz, 2968, 402.23; found, 402.2194 1H), 6.95-6.81 (m, 2H), 1713, 5.58-5.36 (m, 1H), 5.20-5.02 (m, 1H), 1493, 4.38-4.17 (m, 1H), 3.78 (s, 3H), 1242, 3.55-3.08 (m, 1H), 2.10 (h, J = 6.7 Hz, 1H), 1163, 1.45 (s, 9H), 1.38 (d, J = 7.1 Hz, 3H), 1051, 755 cm.sup.-1 1.06 (d, J = 6.2 Hz, 3H), 0.85 (d, J = 6.8 Hz, 3H), 0.74 (d, J = 6.8 Hz, 3H). 52 ESIMS m/z 250.4 ([M + H].sup.+) 53 ESIMS m/z 375.5 ([M + Boc].sup.+) 54 ESIMS m/z 250.4 ([M + H].sup.+) 55 ESIMS m/z 262 ([M + H].sup.+) 56 ESIMS m/z 264.3 ([M + H].sup.+) 57 ESIMS m/z 264.4 ([M + H].sup.+) 58 ESIMS m/z 268 ([M + H].sup.+) 59 ESIMS m/z 266 ([M + H].sup.+) 60 HRMS-ESI (m/z) [M + H].sup.+ calcd for C.sub.17H.sub.28NO.sub.2, 278.2120; found, 278.2115 61 HRMS-ESI (m/z) [M + H].sup.+ calcd for C.sub.17H.sub.26NO.sub.2, 276.1963; found, 276.1960 62 ESIMS m/z 282.2 ([M + H].sup.+) 63 ESIMS m/z 310.2 ([M + H].sup.+) 64 ESIMS m/z 308.2 ([M + H].sup.+) 65 ESIMS m/z 322.2 ([M + H].sup.+) 66 ESIMS m/z 296.2 ([M + H].sup.+) 67 ESIMS m/z 294.2 ([M + H].sup.+) 68 ESIMS m/z 308.2 ([M + H].sup.+) 69 ESIMS m/z 322.2 ([M + H].sup.+) 70 ESIMS m/z 282.1 ([M + H].sup.+) 71 ESIMS m/z 310.2 ([M + H].sup.+) 72 ESIMS m/z 296.2 ([M + H].sup.+) 73 ESIMS m/z 294.2 ([M + H].sup.+) 74 ESIMS m/z 308.1 ([M + H].sup.+) 75 ESIMS m/z 322.2 ([M + H].sup.+) 76 ESIMS m/z 282.2 ([M + H].sup.+) 77 HRMS-ESI (m/z) [M + H].sup.+ calcd for C.sub.18H.sub.30NO.sub.2, 292.2271; found, 292.2268 78 HRMS-ESI (m/z) [M + H].sup.+ calcd for C.sub.20H.sub.32NO.sub.2, 318.2428; found, 318.2525 79 HRMS-ESI (m/z) [M + H].sup.+ calcd for C.sub.19H.sub.30NO.sub.2, 304.2271; found, 304.2267 80 HRMS-ESI (m/z) [M + H].sup.+ calcd for C.sub.17H.sub.28NO.sub.2, 278.2115; found, 278.2112 81 IR (thin HRMS-ESI (m/z) [M + H].sup.+ film) 3383, calcd for C.sub.15H.sub.23FNO.sub.2, 2960, 268.1707; found, 268.1717 1737, 1603, 1509, 1460, 1386, 1223, 1117, 834 cm.sup.-1 82 ESIMS m/z 298.3 ([M + H].sup.+) 83 EIMS m/z 324.9 84 ESIMS m/z 338.3 ([M + H].sup.+) 85 EIMS m/z 324.2 86 EIMS m/z 311.1 87 EIMS m/z 310.2 88 EIMS m/z 337.3 89 EIMS m/z 323.0 90 EIMS m/z 326.2 91 EIMS m/z 311.9 92 ESIMS m/z 310.0 ([M + H].sup.+) 93 EIMS m/z 298.2 94 HRMS-ESI (m/z) [M + H].sup.+ calcd for C.sub.18H.sub.28NO.sub.2, 290.2115; found, 290.2116 95 IR (thin ESIMS m/z 284.1 film) 3451, ([M + H].sup.+) 3381, 2957, 2751, 2626, 2506, 1757, 1515, 1492, 1240, 1214, 1092, 832 cm.sup.-1 96 IR (thin ESIMS m/z 282.2 film) 2959, ([M + H].sup.+) 2928, 1738, 1507, 1235, 1117, 731 cm.sup.-1 97 IR (thin ESIMS m/z 286.2 film) 3386, ([M + H].sup.+) 2961, 1739, 1515, 1238, 1210, 1115 cm.sup.-1 98 ESIMS m/z 282.3 ([M + H].sup.+) 99 ESIMS m/z 298.3 ([M + H].sup.+) 100 ESIMS m/z 298.3 ([M + H].sup.+) 101 ESIMS m/z 294.3 ([M + H].sup.+) 102 ESIMS m/z 294.3 ([M + H].sup.+) 103 HRMS-ESI (m/z) [M + H].sup.+ calcd for C.sub.16H.sub.26NO.sub.3, 280.1907; found, 280.1908 104 HRMS-ESI (m/z) [M + Na].sup.+ calcd for C.sub.17H.sub.27NO.sub.4Na, 382.1832; found, 332.1811 105 HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 12.15 (s, calcd for C.sub.22H.sub.29N.sub.2O.sub.5, 1H), 8.46 (d, J = 8.0 Hz, 1H), 8.01 (d, J = 5.2 Hz, 401.2076; found, 401.2078 1H), 7.27-7.08 (m, 5H), 6.88 (d, J = 5.2 Hz, 1H), 5.56-5.43 (m, 1H), 4.74-4.54 (m, 1H), 3.94 (s, 3H), 2.37 (dd, J = 8.4, 5.7 Hz, 1H), 2.03 (dh, J = 8.4, 6.6 Hz, 1H), 1.32 (d, J = 7.2 Hz, 3H), 1.13 (d, J = 6.3 Hz, 3H), 0.95 (d, J = 6.6 Hz, 3H), 0.71 (d, J = 6.7 Hz, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 171.67, 168.64, 155.38, 148.77, 140.46, 139.69, 130.49, 129.58, 127.91, 126.49, 109.45, 72.39, 57.96, 56.07, 48.05, 29.19, 21.30, 20.17, 18.93, 18.06. 106 HRMS-ESI (m/z) [M + H]+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 12.17 (s, calcd for C.sub.24H.sub.31N.sub.2O.sub.5, 1H), 8.52 (d, J = 8.0 Hz, 1H), 8.01 (d, J = 5.2 Hz, 427.2233; found, 427.2235 1H), 7.31-7.12 (m, 5H), 6.88 (d, J = 5.2 Hz, 1H), 5.37 (qd, J = 6.3, 3.9 Hz, 1H), 4.81-4.58 (m, 1H), 3.94 (s, 3H), 2.42 (dd, J = 10.3, 4.1 Hz, 1H), 2.25-2.16 (m, 1H), 1.88 (dtd, J = 11.2, 7.2, 3.3 Hz, 1H), 1.69-1.50 (m, 3H), 1.49 (d, J = 7.2 Hz, 3H), 1.47-1.30 (m, 2H), 1.24-1.13 (m, 1H), 1.08 (d, J = 6.4 Hz, 3H), 0.99-0.85 (m, 1H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 171.60, 168.73, 155.39, 148.80, 140.63, 140.49, 130.45, 129.44, 127.93, 126.45, 109.49, 73.59, 56.60, 56.07, 48.21, 42.11, 31.63, 31.45, 25.07, 24.52, 18.73, 18.22. 107 HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (300 MHz, CDCl.sub.3) .delta. 12.16 (s, calcd for C.sub.22H.sub.29N.sub.2O.sub.5, 1H), 8.50 (d, J = 7.9 Hz, 1H), 8.00 (d, J = 5.2 Hz, 401.2076; found, 401.2073 1H), 7.38-7.17 (m, 3H), 7.13-7.04 (m, 2H), 6.88 (d, J = 5.2 Hz, 1H), 5.44 (dq, J = 8.6, 6.3 Hz, 1H), 4.81-4.59 (m, 1H), 3.95 (s, 3H), 2.72 (dd, J = 8.6, 6.5 Hz, 1H), 2.24-2.00 (m, 1H), 1.55 (d, J = 7.2 Hz, 3H), 1.11 (d, J = 6.3 Hz 3H), 0.86 (d, J = 6.8 Hz, 3H), 0.76 (d, J = 6.7 Hz, 3H). .sup.13C NMR (75 MHz, CDCl.sub.3) .delta. 171.73, 168.72, 155.37, 148.75, 140.50, 138.53, 130.49, 129.78, 127.93, 126.66, 109.45, 73.04, 56.60, 56.11, 48.21, 28.31, 21.31, 18.65, 18.35, 17.76. 108 HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 12.18 (s, calcd for C.sub.23H.sub.29N.sub.2O.sub.5 1H), 8.50 (d, J = 8.1 Hz, 1H), 8.00 (d, J = 5.2 Hz, 413.2071; found, 413.2070 1H), 7.12-7.05 (m, 4H), 6.88 (d, J = 5.2 Hz, 1H), 5.42-5.24 (m, 1H), 4.82-4.63 (m, 1H), 3.95 (s, 3H), 2.32 (s, 3H), 1.99 (dd, J = 10.1, 7.0 Hz, 1H), 1.52 (d, J = 7.2 Hz, 3H), 1.18 (d, J = 6.4 Hz, 3H), 1.15-1.06 (m, 1H), 0.70-0.61 (m, 1H), 0.44-0.29 (m, 2H), -0.01--0.10 (m, 1H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 171.66, 168.63, 155.40, 148.79, 140.43, 138.48, 136.16, 130.58, 128.94, 128.25, 109.44, 76.20, 56.06, 55.24, 48.15, 21.01, 18.39, 18.13, 12.99, 6.94, 2.89. 109 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 12.17 (d, film) 3370, calcd for C.sub.23H.sub.31N.sub.2O.sub.5, J = 0.6 Hz, 1H), 8.51 (d, J = 7.9 Hz, 2960, 415.2227; found, 415.2222 1H), 8.00 (d, J = 5.2 Hz, 1H), 1732, 7.11-7.05 (m, 2H), 7.00-6.95 (m, 2H), 1649, 6.88 (d, J = 5.2 Hz, 1H), 5.42 (dq, J = 8.6, 1527, 6.3 Hz, 1H), 4.75-4.65 (m, 1H), 1481, 3.94 (s, 3H), 2.68 (dd, J = 8.6, 6.5 Hz, 1H), 1451, 2.31 (s, 3H), 2.09 (h, J = 6.7 Hz, 1H), 1263, 1.56 (d, J = 7.2 Hz, 3H), 1.11 (d, J = 6.2 Hz, 1150, 3H), 0.85 (d, J = 6.8 Hz, 3H), 1048, 799, 0.76 (d, J = 6.8 Hz, 3H). 730 cm.sup.-1 .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 171.72, 168.74, 155.39, 148.79, 140.47, 136.11, 135.40, 130.54, 129.64, 128.64, 109.47, 73.12, 56.22, 56.07, 48.23, 28.28, 21.32, 20.99, 18.65, 18.33, 17.75. 110 HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 12.15 (s, calcd for C.sub.22H.sub.28FN.sub.2O.sub.5, 1H), 8.61-8.38 (m, 1H), 419.1977; found, 419.1978 8.06-7.94 (m, 1H), 7.12-6.82 (m, 5H), 5.51-5.33 (m, 1H), 4.75-4.60 (m, 1H), 3.95 (s, 3H), 2.77-2.63 (m, 1H), 2.16-1.99 (m, 1H), 1.59-1.47 (m, 3H), 1.16-1.04 (m, 3H), 0.94-0.83 (m, 3H), 0.79-0.71 (m, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -116.41, -116.47. 111 HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 12.15 (s, calcd for C.sub.22H.sub.26FN.sub.2O.sub.5, 1H), 8.46 (d, J = 8.1 Hz,

1H), 8.00 (d, J = 5.2 Hz, 417.1821; found, 417.1813 1H), 7.21-7.07 (m, 2H), 7.02-6.92 (m, 2H), 6.88 (d, J = 5.2 Hz, 1H), 5.37-5.25 (m, 1H), 4.85-4.60 (m, 1H), 3.95 (s, 3H), 2.03 (dd, J = 10.2, 6.6 Hz, 1H), 1.51 (d, J = 7.2 Hz, 3H), 1.19 (d, J = 6.4 Hz, 3H), 1.16-1.03 (m, 1H), 0.74-0.62 (m, 1H), 0.49-0.29 (m, 2H), -0.02--0.12 (m, 1H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -116.42. 112 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (300 MHz, CDCl.sub.3) .delta. 12.16 (s, film) 3372, calcd for C.sub.24H.sub.33N.sub.2O.sub.5, 1H), 8.51 (d, J = 7.9 Hz, 1H), 8.00 (d, J = 5.2 Hz, 2962, 429.2389; found, 429.2385 1H), 7.38-7.00 (m, 5H), 2934, 6.88 (d, J = 5.2 Hz, 1H), 2879, 5.59-5.37 (m, 1H), 4.70 (p, J = 7.2 Hz, 1H), 1734, 3.95 (s, 3H), 2.97 (dd, J = 8.5, 6.4 Hz, 1H), 1650, 1.55 (d, J = 7.2 Hz, 3H), 1576, 1.51-1.31 (m, 5H), 1.12 (d, J = 6.3 Hz, 3H), 1528, 0.93 (t, J = 7.4 Hz, 3H), 0.77 (t, J = 7.2 Hz, 1481, 3H). 1452, 1324, 1280, 1264, 1213, 1149, 1059, 954, 802, 737, 705 cm.sup.-1. 113 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (300 MHz, CDCl.sub.3) .delta. 12.17 (s, film) 3370, calcd for C.sub.24H.sub.31N.sub.2O.sub.5, 1H), 8.48 (t, J = 8.9 Hz, 1H), 8.00 (d, J = 5.9 Hz, 2943, 427.2233; found, 427.2237 1H), 7.33-7.03 (m, 5H), 2868, 6.93-6.83 (m, 1H), 5.41-5.26 (m, 1731, 1H), 4.80-4.58 (m, 1H), 3.95 (s, 3H), 1648, 2.78 (dd, J = 10.1, 5.9 Hz, 1H), 1527, 2.33-2.11 (m, 2H), 1.99-1.80 (m, 2H), 1450, 1.69-1.56 (m, 2H), 1.52 (dd, J = 7.2 Hz, 1263, 3H), 1.44-1.16 (m, 4H), 1.13 (d, J = 6.5 Hz, 1144, 2H). 1038, 799, 734, 702 cm.sup.-1. 114 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 12.94 (s, film) 3254, calcd for C.sub.24H.sub.31N.sub.2O.sub.4S, 1H), 10.69 (s, 1H), 7.98 (s, 1H), 2947, 443.1999; found, 443.2026 7.26-7.18 (m, 4H), 7.14-7.08 (m, 1H), 2867, 6.88 (s, 1H), 5.43-5.25 (m, 1H), 5.07 (dp, J = 17.6, 1729, 7.2 Hz, 1H), 3.97 (d, J = 3.1 Hz, 1512, 3H), 2.79 (dd, J = 9.9, 6.0 Hz, 1H), 1485, 2.45-2.27 (m, 1H), 2.27-2.12 (m, 1H), 1273, 2.00-1.77 (m, 1H), 1.61 (d, J = 7.1 Hz, 1207, 730 cm.sup.-1 3H), 1.57-1.39 (m, 4H), 1.35-1.23 (m, 2H), 1.14 (d, J = 6.4 Hz, 3H). 115 IR HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 12.94 (s, (CDCl3) calcd for C.sub.24H.sub.30N.sub.2O.sub.4S, 1H), 10.71 (s, 1H), 8.01 (d, J = 15.0 Hz, 2951, 465.1818; found, 465.1830 1H), 7.22-7.17 (m, 3H), 7.15 (dd, J = 6.7, 2868, 3.0 Hz, 2H), 6.89 (d, J = 5.0 Hz, 1733, 1H), 5.39 (qd, J = 6.4, 4.0 Hz, 1H), 1581, 5.12-5.03 (m, 1H), 3.97 (s, 3H), 2.41 (dd, J = 10.4, 1514, 4.0 Hz, 1H), 2.25-2.14 (m, 1486, 1H), 1.95-1.84 (m, 1H), 1454, 1.69-1.59 (m, 1H), 1.56 (d, J = 7.2 Hz, 3H), 1377, 1.54-1.45 (m, 2H), 1.44-1.28 (m, 2H), 1342, 1.19 (dq, J = 12.3, 9.1 Hz, 1H), 1.09 (d, 1274, J = 6.4 Hz, 3H), 0.92 (ddt, J = 12.5, 1249, 10.0, 8.5 Hz, 1H). 1211, 1131, 1095, 992, 913, 860, 801, 736, 703 cm.sup.-1 116 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 12.13 (s, film) 3369, calcd for C.sub.23H.sub.29FN.sub.2NaO.sub.5, 1H), 8.46 (d, J = 8.0 Hz, 1H), 8.02 (d, J = 5.2 Hz, 2967, 455.1953; found, 455.1947 1H), 7.22 (dd, J = 8.7, 6.0 Hz, 1733, 1H), 6.89 (d, J = 5.2 Hz, 1H), 6.83 (dd, 1650, J = 9.9, 2.7 Hz, 1H), 6.73 (td, J = 8.5, 1529, 2.9 Hz, 1H), 5.49-5.41 (m, 1H), 1481, 4.69 (p, J = 7.3 Hz, 1H), 3.95 (s, 3H), 1264, 954, 2.69 (dd, J = 9.2, 5.0 Hz, 1H), 2.27 (s, 3H), 801, 733 cm.sup.-1 2.07-1.86 (m, 1H), 1.43 (d, J = 7.2 Hz, 3H), 1.07 (d, J = 6.3 Hz, 3H), 0.99 (d, J = 6.6 Hz, 3H), 0.68 (d, J = 6.7 Hz, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 171.56, 168.72, 160.94 (d, J = 244.1 Hz), 155.46, 148.86, 140.50, 139.36 (d, J = 7.2 Hz), 134.57 (d, J = 3.3 Hz), 130.48, 129.32 (d, J = 8.2 Hz), 116.44 (d, J = 20.5 Hz), 112.67 (d, J = 20.5 Hz), 109.54, 72.65, 56.10, 50.65, 48.12, 30.45, 21.00, 20.72, 20.47, 18.37, 18.16. .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.61. 117 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 12.14 (s, film) 3372, calcd for C.sub.25H.sub.33FN.sub.2NaO.sub.5, 1H), 8.47 (d, J = 8.1 Hz, 1H), 8.03 (d, J = 5.2 Hz, 2963, 483.2266; found, 483.2262 1H), 7.28-7.21 (m, 1H), 1732, 6.89 (d, J = 5.2 Hz, 1H), 6.82 (dd, J = 9.9, 1649, 2.8 Hz, 1H), 6.73 (td, J = 8.5, 2.9 Hz, 1528, 1H), 5.40 (qt, J = 6.2, 3.0 Hz, 1H), 1450, 4.71 (p, J = 7.3 Hz, 1H), 3.95 (s, 3H), 1263, 2.90 (dd, J = 10.0, 4.3 Hz, 1H), 2.27 (s, 1060, 954, 3H), 1.63-1.46 (m, 4H), 800, 731 cm.sup.-1 1.46-1.32 (m, 1H), 1.15-0.83 (m, 9H), 0.65 (t, J = 7.4 Hz, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 171.62, 168.78, 160.93 (d, J = 244.2 Hz), 155.49, 148.90, 140.52, 139.40 (d, J = 7.2 Hz), 134.65 (d, J = 3.2 Hz), 130.47, 129.74 (d, J = 7.9 Hz), 116.41 (d, J = 20.6 Hz), 112.73 (d, J = 20.5 Hz), 109.57, 72.33, 56.11, 48.24, 41.62, 29.30, 21.72, 21.09, 20.60, 18.28, 18.20, 10.79, 9.43. .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.60. 118 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 12.14 (s, film) 3372, calcd for C.sub.25H.sub.31FN.sub.2NaO.sub.5, 1H), 8.47 (d, J = 8.1 Hz, 1H), 8.02 (d, J = 5.2 Hz, 2951, 481.2109; found, 481.2106 1H), 7.22 (dd, J = 8.7, 6.0 Hz, 1732, 1H), 6.89 (d, J = 5.2 Hz, 1H), 6.82 (dd, 1649, J = 9.8, 2.9 Hz, 1H), 6.71 (td, J = 8.5, 1528, 2.9 Hz, 1H), 5.34 (qd, J = 6.4, 4.1 Hz, 1263, 1H), 4.71 (p, J = 7.3 Hz, 1H), 3.95 (s, 1060, 952, 3H), 2.79 (dd, J = 10.3, 4.3 Hz, 1H), 911, 800, 2.28 (s, 3H), 2.20-2.08 (m, 1H), 730 cm.sup.-1 1.90 (dtd, J = 11.3, 7.2, 3.6 Hz, 1H), 1.77-1.14 (m, 9H), 1.08 (d, J = 6.3 Hz, 3H), 0.85 (ddt, J = 12.4, 10.2, 8.4 Hz, 1H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 171.50, 168.76, 160.89 (d, J = 244.1 Hz), 155.47, 148.87, 140.51, 138.79 (d, J = 7.3 Hz), 135.16 (d, J = 3.3 Hz), 130.47, 129.60 (d, J = 8.0 Hz), 116.40 (d, J = 20.4 Hz), 112.67 (d, J = 20.6 Hz), 109.56, 73.88, 56.11, 49.39, 48.22, 42.94, 31.60, 31.38, 25.08, 24.42, 20.60, 18.19, 18.13. .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.66. 119 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 12.14 (s, film) 3372, calcd for C.sub.26H.sub.34FN.sub.2O.sub.5, 1H), 8.47 (d, J = 8.1 Hz, 1H), 8.02 (d, J = 5.2 Hz, 2928, 473.2446; found, 473.2440 1H), 7.23 (dd, J = 8.7, 6.0 Hz, 1732, 1H), 6.89 (d, J = 5.2 Hz, 1H), 6.82 (dd, 1649, J = 9.9, 2.9 Hz, 1H), 6.74 (td, J = 8.5, 1528, 2.9 Hz, 1H), 5.50-5.39 (m, 1H), 1448, 4.70 (p, J = 7.3 Hz, 1H), 3.95 (s, 3H), 1263, 2.75 (dd, J = 9.3, 4.8 Hz, 1H), 2.26 (s, 3H), 1060, 954, 1.87 (dt, J = 12.7, 3.2 Hz, 1H), 910, 730 cm.sup.-1 1.80-1.70 (m, 1H), 1.70-1.52 (m, 3H), 1.45 (d, J = 7.2 Hz, 3H), 1.35-1.15 (m, 2H), 1.15-0.85 (m, 6H), 0.76 (qd, J = 12.2, 3.6 Hz, 1H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 171.59, 168.75, 160.90 (d, J = 243.9 Hz), 155.48, 148.86, 140.51, 139.44 (d, J = 7.2 Hz), 134.60 (d, J = 3.3 Hz), 130.48, 129.40 (d, J = 8.0 Hz), 116.37 (d, J = 20.5 Hz), 112.71 (d, J = 20.5 Hz), 109.56, 71.90, 56.11, 49.65, 48.16, 40.26, 31.30, 30.80, 26.44, 26.40, 26.30, 20.72, 18.19, 18.19. .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.64. 120 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 12.13 (d, film) 3372, calcd for C.sub.24H.sub.32FN.sub.2O.sub.5, J = 3.1 Hz, 1H), 8.45 (t, J = 6.7 Hz, 2965, 447.2290; found, 447.2296 1H), 8.02 (dd, J = 5.2, 3.5 Hz, 1H), 1734, 7.22 (ddd, J = 8.8, 6.1, 4.0 Hz, 1H), 6.89 (dd, 1650, J = 5.3, 1.7 Hz, 1H), 6.82 (dd, J = 10.0, 1529, 2.9 Hz, 1H), 6.73 (qd, J = 8.7, 2.9 Hz, 1265, 954, 1H), 5.44 (tdd, J = 9.1, 6.4, 3.5 Hz, 1H), 801, 734 cm.sup.-1 4.68 (dp, J = 10.9, 7.3 Hz, 1H), 3.95 (s, 3H), 2.78 (ddd, J = 48.5, 9.2, 4.9 Hz, 1H), 2.27 (d, J = 3.9 Hz, 3H), 1.87-1.33 (m, 4H), 1.26 (s, 1H), 1.23-0.76 (m, 7H), 0.76-0.60 (m, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.60, -117.64. 121 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 12.12 (s, film) 3368, calcd for C.sub.24H.sub.30FN.sub.2O.sub.5, 1H), 8.38 (d, J = 8.1 Hz, 1H), 7.99 (d, J = 5.1 Hz, 2938, 445.2133; found, 445.2130 1H), 7.06 (dd, J = 8.6, 5.9 Hz, 1733, 1H), 6.87 (d, J = 5.2 Hz, 1H), 6.80 (dd, 1648, J = 9.9, 2.8 Hz, 1H), 6.74 (td, J = 8.5, 1528, 2.9 Hz, 1H), 5.16 (p, J = 6.3 Hz, 1H), 1481, 4.58 (p, J = 7.3 Hz, 1H), 3.94 (s, 3H), 1439, 3.03 (dd, J = 10.4, 6.6 Hz, 1H), 1263, 953, 2.70-2.57 (m, 1H), 2.34 (s, 3H), 800, 730 cm.sup.-1 2.23-2.10 (m, 1H), 1.86-1.55 (m, 4H), 1.45-1.34 (m, 1H), 1.28-1.22 (m, 3H), 1.19 (d, J = 6.3 Hz, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 171.39, 168.64, 160.91 (d, J = 243.9 Hz), 155.43, 148.81, 140.45, 139.10 (d, J = 6.7 Hz), 134.12 (d, J = 3.2 Hz), 130.49, 128.52 (d, J = 5.2 Hz), 116.50 (d, J = 20.4 Hz), 112.72 (d, J = 20.7 Hz), 109.49, 74.20, 56.09, 50.86, 47.99, 37.76, 29.39, 26.99, 20.45, 18.51, 18.19, 17.92. .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.49. 122 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 12.13 (s, film) 3369, calcd for C.sub.25H.sub.32FN.sub.2O.sub.5, 1H), 8.41 (d, J = 8.2 Hz, 1H), 7.98 (d, J = 5.2 Hz, 2946, 459.2290; found, 459.2318 1H), 7.09 (dd, J = 8.6, 5.9 Hz, 1732, 1H), 6.92-6.80 (m, 2H), 6.77 (dd, J = 9.9, 1648, 2.8 Hz, 1H), 5.31 (p, J = 6.4 Hz, 1528, 1H), 4.75-4.64 (m, 1H), 3.95 (s, 3H), 1262, 3.10 (dt, J = 7.1, 5.4 Hz, 1H), 2.26 (s, 1153, 953, 3H), 2.20-2.06 (m, 1H), 1.87 (qdd, J = 11.1, 800, 730 cm.sup.-1 8.9, 7.1, 3.8 Hz, 1H), 1.69-1.06 (m, 12H), 0.98-0.82 (m, 1H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 171.59, 168.65, 160.84 (d, J = 244.2 Hz), 155.41, 148.81, 140.44, 139.16 (d, J = 7.4 Hz), 134.99 (d, J = 3.0 Hz), 130.48, 129.07 (d, J = 8.3 Hz), 116.78 (d, J = 20.4 Hz), 112.48 (d, J = 20.6 Hz), 109.49, 75.73, 56.09, 48.21, 48.21, 43.47, 31.50, 31.09, 25.12, 24.13, 20.72, 18.23, 17.26. .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.47. 123 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 12.14 (s, film) 3371, calcd for C.sub.26H.sub.34FN.sub.2O.sub.5, 1H), 8.47 (d, J = 8.1 Hz, 1H), 7.99 (d, J = 5.2 Hz, 2928, 473.2446; found, 473.2467 1H), 7.05 (dd, J = 8.6, 5.9 Hz, 1733, 1H), 6.92-6.75 (m, 4H), 5.40 (dq, J = 9.0, 1650, 6.3 Hz, 1H), 4.77-4.68 (m, 1H), 1528, 3.95 (s, 3H), 3.12 (dd, J = 9.0, 6.1 Hz, 1450, 1H), 2.29 (s, 3H), 1.82-1.59 (m, 3H), 1264, 1.53 (dd, J = 21.9, 7.2 Hz, 5H), 1155, 954, 1.28-0.78 (m, 8H). 800, 732 cm.sup.-1 .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 171.67, 168.67, 160.89 (d, J = 244.6 Hz),

155.42, 148.82, 140.47, 139.76 (d, J = 7.6 Hz), 133.87 (d, J = 3.3 Hz), 130.50, 129.20 (d, J = 7.2 Hz), 116.93 (d, J = 20.6 Hz), 112.37 (d, J = 20.7 Hz), 109.50, 73.49, 56.10, 49.06, 48.20, 40.18, 31.47, 29.14, 26.60, 26.55, 26.32, 20.95, 18.38, 17.98. .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.35. 124 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 12.13 (s, film) 3366, calcd for C.sub.23H.sub.30FN.sub.2O.sub.5, 1H), 8.45 (d, J = 8.0 Hz, 1H), 7.99 (d, J = 5.2 Hz, 2961, 433.2133; found, 433.2129 1H), 7.05 (dd, J = 8.6, 5.9 Hz, 1734, 1H), 6.93-6.77 (m, 3H), 5.38 (dq, J = 8.9, 1650, 6.3 Hz, 1H), 4.76-4.65 (m, 1H), 1529, 3.95 (s, 3H), 3.09 (dd, J = 8.9, 6.5 Hz, 1264, 1H), 2.29 (s, 3H), 2.11 (h, J = 6.8 Hz, 1153, 1H), 1.55 (d, J = 7.2 Hz, 3H), 1.08 (d, J = 6.2 Hz, 1049, 955, 3H), 0.86 (d, J = 6.8 Hz, 3H), 801, 735 cm.sup.-1 0.78 (d, J = 6.7 Hz, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.30. 125 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 12.13 (s, film) 3368, calcd for C.sub.25H.sub.34FN.sub.2O.sub.5, 1H), 8.42 (d, J = 8.2 Hz, 1H), 7.98 (d, J = 5.3 Hz, 2962, 461.2446; found, 461.2442 1H), 7.10 (dd, J = 8.7, 5.9 Hz, 1733, 1H), 6.88 (d, J = 5.1 Hz, 1H), 6.83 (td, 1650, J = 8.3, 2.8 Hz, 1H), 6.77 (dd, J = 9.9, 1528, 2.9 Hz, 1H), 5.46-5.40 (m, 1H), 1263, 4.75-4.66 (m, 1H), 3.95 (d, J = 2.2 Hz, 3H), 1154, 3.27 (t, J = 7.7 Hz, 1H), 2.27 (s, 2H), 1057, 954, 1.67-1.24 (m, 8H), 1.14-0.82 (m, 800, 733 cm.sup.-1 7H), 0.76 (t, J = 7.4 Hz, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.38. 126 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 12.13 (d, film) 3369, calcd for C.sub.24H.sub.32FN.sub.2O.sub.5, J = 4.6 Hz, 1H), 8.50-8.39 (m, 1H), 2964, 447.2290; found, 447.2302 7.99 (dd, J = 5.3, 2.8 Hz, 1H), 1733, 7.07 (ddd, J = 8.9, 5.9, 3.1 Hz, 1H), 1649, 6.93-6.75 (m, 3H), 5.40 (ddq, J = 21.8, 9.3, 1528, 6.3 Hz, 1H), 4.77-4.64 (m, 1H), 1262, 3.95 (s, 3H), 3.16 (ddd, J = 24.5, 8.9, 6.4 Hz, 1056, 953, 1H), 2.35-2.26 (m, 3H), 800, 730 cm.sup.-1 1.94-1.73 (m, 1H), 1.55 (t, J = 6.9 Hz, 3H), 1.52-1.33 (m, 1H), 1.08 (dd, J = 9.4, 6.2 Hz, 3H), 1.01-0.72 (m, 7H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.29, -117.34. 127 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 12.14 (s, film) 3369, calcd for C.sub.24H.sub.29FN.sub.2O.sub.5, 1H), 8.46 (d, J = 8.1 Hz, 1H), 8.00 (dd, 2939, 467.1953; found, 467.1940 J = 8.2, 5.2 Hz, 1H), 7.01 (ddd, J = 9.3, 1733, 4.6, 2.2 Hz, 1H), 6.88 (d, J = 5.2 Hz, 1649, 1H), 6.82 (dd, J = 8.0, 3.4 Hz, 2H), 1438, 5.12 (p, J = 6.3 Hz, 1H), 4.78-4.64 (m, 1261, 1H), 3.95 (s, 3H), 3.14 (dd, J = 10.0, 1039, 953, 7.4 Hz, 1H), 2.74 (h, J = 8.3 Hz, 1H), 800, 729 cm.sup.-1 2.33 (s, 3H), 2.23-2.06 (m, 1H), 2.05-1.57 (m, 4H), 1.54 (d, J = 7.1 Hz, 3H), 1.45-1.33 (m, 1H), 1.09 (d, J = 6.3 Hz, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.25. 128 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 12.14 (s, film) 3369, calcd for C.sub.25H.sub.31FN.sub.2NaO.sub.5, 1H), 8.45 (d, J = 7.7 Hz, 1H), 8.02 (d, J = 5.1 Hz, 2951, 481.2109; found, 481.2105 1H), 7.30 (dd, J = 8.7, 6.1 Hz, 1735, 1H), 6.90 (d, J = 5.2 Hz, 1H), 6.82 (dd, 1650, J = 9.9, 2.9 Hz, 1H), 6.71 (td, J = 8.5, 1529, 2.9 Hz, 1H), 5.33 (qd, J = 6.3, 3.4 Hz, 1264, 953, 1H), 4.71 (p, J = 7.3 Hz, 1H), 3.96 (s, 733 cm.sup.-1 3H), 2.78 (dd, J = 10.5, 3.7 Hz, 1H), 2.29 (s, 3H), 2.28-2.16 (m, 1H), 1.92 (ddq, J = 10.8, 7.1, 3.4 Hz, 1H), 1.73-1.60 (m, 1H), 1.60-1.47 (m, 5H), 1.47-1.31 (m, 2H), 1.31-1.15 (m, 1H), 1.04 (d, J = 6.4 Hz, 3H), 0.92-0.77 (m, 1H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.71. 129 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 12.15 (s, film) 3372, calcd for C.sub.26H.sub.34FN.sub.2O.sub.5, 1H), 8.42 (d, J = 7.7 Hz, 1H), 8.02 (d, J = 5.2 Hz, 2928, 473.2446; found, 473.2455 1H), 7.30 (dd, J = 8.7, 6.1 Hz, 1733, 1H), 6.90 (d, J = 5.2 Hz, 1H), 6.81 (dd, 1527, J = 9.9, 2.8 Hz, 1H), 6.68 (td, J = 8.5, 1263, 955, 2.9 Hz, 1H), 5.45 (qd, J = 6.2, 4.0 Hz, 800, 730 cm.sup.-1 1H), 4.70 (p, J = 7.2 Hz, 1H), 3.96 (s, 3H), 2.73 (dd, J = 9.9, 4.1 Hz, 1H), 2.26 (s, 3H), 1.92 (dt, J = 12.9, 3.2 Hz, 1H), 1.80-1.53 (m, 4H), 1.51 (d, J = 7.2 Hz, 3H), 1.35-1.03 (m, 4H), 1.00 (d, J = 6.3 Hz, 3H), 0.95 (td, J = 12.1, 3.7 Hz, 1H), 0.74 (qd, J = 12.2, 3.6 Hz, 1H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.72. 130 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 12.12 (s, film) 3372, calcd for C.sub.23H.sub.30FN.sub.2O.sub.5, 1H), 8.43 (d, J = 8.3 Hz, 1H), 8.02 (d, J = 5.2 Hz, 2964, 433.2133; found, 433.2130 1H), 7.33-7.23 (m, 1H), 1734, 6.90 (d, J = 5.2 Hz, 1H), 6.82 (dd, J = 10.0, 1528, 3.0 Hz, 1H), 6.66 (td, J = 8.5, 2.9 Hz, 1264, 954, 1H), 5.44 (qd, J = 6.3, 4.0 Hz, 1H), 801, 732 cm.sup.-1 4.70 (p, J = 7.3 Hz, 1H), 3.96 (s, 3H), 2.68-2.62 (m, 1H), 2.27 (s, 3H), 2.15-1.82 (m, 1H), 1.50 (d, J = 7.2 Hz, 3H), 1.02 (dd, J = 6.4, 2.1 Hz, 6H), 0.67 (d, J = 6.7 Hz, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.67. 131 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 12.16 (s, film) 3369, calcd for C.sub.24H.sub.33N.sub.2O.sub.5, 1H), 8.49 (d, J = 8.0 Hz, 1H), 8.01 (d, J = 5.2 Hz, 2968, 451.2203; found, 451.2190 1H), 7.15 (d, J = 7.9 Hz, 1H), 1732, 6.93 (d, J = 1.8 Hz, 1H), 1649, 6.92-6.85 (m, 2H), 5.44 (qd, J = 6.2, 4.1 Hz, 1H), 1527, 4.76-4.60 (m, 1H), 3.94 (s, 3H), 1263, 800, 2.70 (dd, J = 9.2, 5.0 Hz, 1H), 2.27 (s, 3H), 730 cm.sup.-1 2.24 (s, 3H), 2.02 (dp, J = 9.1, 6.7 Hz, 1H), 1.42 (d, J = 7.2 Hz, 3H), 1.09 (d, J = 6.3 Hz, 3H), 0.99 (d, J = 6.6 Hz, 3H), 0.70 (d, J = 6.7 Hz, 3H). 132 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 12.17 (s, film) 3369, calcd for C.sub.26H.sub.35N.sub.2O.sub.5, 1H), 8.50 (d, J = 8.0 Hz, 1H), 8.02 (d, J = 5.2 Hz, 2947, 455.2540; found, 455.2536 1H), 7.16 (d, J = 7.9 Hz, 1H), 2868, 6.93 (d, J = 1.8 Hz, 1H), 2256, 6.91-6.85 (m, 2H), 5.33 (qd, J = 6.3, 4.2 Hz, 1H), 1713, 4.70 (p, J = 7.4 Hz, 1H), 3.94 (s, 3H), 1527, 2.80 (dd, J = 10.2, 4.2 Hz, 1H), 2.26 (s, 1263, 730 cm.sup.-1 3H), 2.26 (s, 3H), 2.17 (dddd, J = 17.0, 10.2, 6.8, 3.1 Hz, 1H), 1.89 (dtd, J = 11.0, 7.1, 3.3 Hz, 1H), 1.69-1.31 (m, 8H), 1.21 (dq, J = 12.3, 9.2 Hz, 1H), 1.09 (d, J = 6.4 Hz, 3H), 0.92-0.81 (m, 1H). 133 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 12.17 (d, film) 3369, calcd for C.sub.27H.sub.37N.sub.2O.sub.5, J = 0.6 Hz, 1H), 8.50 (d, J = 8.0 Hz, 2925, 491.2516; found, 491.2520 1H), 8.02 (d, J = 5.2 Hz, 1H), 7.16 (d, J = 7.9 Hz, 2850, 1H), 6.92 (d, J = 1.9 Hz, 1H), 1731, 6.91-6.86 (m, 2H), 5.44 (qd, J = 6.3, 1527, 4.7 Hz, 1H), 4.75-4.64 (m, 1H), 1262, 729 cm.sup.-1 3.94 (s, 3H), 2.76 (dd, J = 9.3, 4.8 Hz, 1H), 2.27 (s, 3H), 2.23 (s, 3H), 1.87 (dt, J = 12.5, 3.3 Hz, 1H), 1.78-1.47 (m, 4H), 1.44 (d, J = 7.2 Hz, 3H), 1.39-1.14 (m, 2H), 1.05 (d, J = 6.3 Hz, 3H), 1.03-0.69 (m, 4H). 134 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. film) 3369, calcd for C.sub.25H.sub.35N.sub.2O.sub.5, 12.15 (dd, J = 3.6, 0.6 Hz, 1H), 2964, 443.2540; found, 443.2562 8.52-8.44 (m, 1H), 8.01 (t, J = 5.1 Hz, 1H), 2933, 7.15 (dd, J = 7.9, 2.0 Hz, 1H), 2875, 6.95-6.91 (m, 1H), 6.91-6.85 (m, 2H), 1732, 5.49-5.40 (m, 1H), 4.73-4.61 (m, 1H), 1527, 3.94 (s, 3H), 2.88-2.70 (m, 1H), 1263, 800, 2.28-2.22 (m, 6H), 1.91-1.68 (m, 1H), 730 cm.sup.-1 1.49-1.33 (m, 3H), 1.14-0.64 (m, 11H). 135 IR (thin ESIMS m/z 419.1 .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 12.14 (s, film) 3370, ([M + H].sup.+) 1H), 8.45 (d, J = 8.0 Hz, 1H), 8.00 (d, J = 5.2 Hz, 2961, 1H), 7.09-6.99 (m, 2H), 1733, 6.99-6.90 (m, 2H), 6.89 (d, J = 5.2 Hz, 1648, 1H), 5.40 (dq, J = 8.4, 6.3 Hz, 1H), 1575, 4.69 (p, J = 7.3 Hz, 1H), 3.96 (s, 3H), 1528, 3.71 (t, J = 6.9 Hz, 1H), 2.70 (dd, J = 8.3, 1509, 6.8 Hz, 1H), 1.54 (d, J = 7.1 Hz, 1480, 3H), 1.10 (d, J = 6.3 Hz, 3H), 0.87 (d, J = 6.8 Hz, 1453, 3H), 0.74 (d, J = 6.7 Hz, 3H). 1437, .sup.13C NMR (126 MHz, CDCl.sub.3) .delta. 171.63, 1307, 168.72, 168.30, 161.72 (d, J = 244.8 Hz), 1280, 155.40, 155.06, 150.14, 148.78, 1261, 140.49, 139.14, 134.23 (d, J = 3.3 Hz), 1241, 131.01 (d, J = 7.7 Hz), 130.46, 1150, 801 cm.sup.-1 114.80 (d, J = 21.1 Hz), 109.47, 108.37, 72.80, 56.10, 55.83, 50.65, 48.19, 47.95, 28.35, 27.05, 23.40, 21.21, 18.75, 18.32, 17.41. 136 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 12.92 (s, film) 3131, calcd for C.sub.23H.sub.30FN.sub.2O.sub.4S, 1H), 10.79-10.61 (m, 1H), 7.98 (d, J = 5.1 Hz, 2959, 449.1905; found, 449.1906 1H), 7.05 (dd, J = 8.6, 5.9 Hz, 1748, 1H), 6.85 (ddt, J = 17.1, 9.5, 4.7 Hz, 1511, 3H), 5.40 (dq, J = 13.0, 6.4 Hz, 1H), 1479, 5.09 (p, J = 7.2 Hz, 1H), 3.97 (s, 3H), 1280, 3.11 (dd, J = 9.0, 6.3 Hz, 1H), 2.30 (s, 1207, 3H), 2.13 (dt, J = 13.5, 6.8 Hz, 1H), 1142, 797 cm.sup.-1 1.64 (d, J = 7.1 Hz, 3H), 1.09 (d, J = 6.3 Hz, 3H), 0.86 (d, J = 6.7 Hz, 3H), 0.79 (d, J = 6.8 Hz, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.20. 137 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 12.15 (d, film) 3372, calcd for C.sub.25H.sub.34FN.sub.2O.sub.6, J = 0.6 Hz, 1H), 8.47 (d, J = 8.1 Hz, 2963, 477.2395; found, 477.2392 1H), 8.02 (d, J = 5.3 Hz, 1H), 7.18 (dd, 1731, J = 8.5, 6.9 Hz, 1H), 6.89 (d, J = 5.1 Hz, 1649, 1H), 6.57 (dd, J = 11.0, 2.5 Hz, 1528, 1H), 6.51 (td, J = 8.4, 2.6 Hz, 1H), 1450, 5.40 (qd, J = 6.2, 4.5 Hz, 1H), 1263, 4.75-4.62 (m, 1H), 3.95 (s, 3H), 3.77 (s, 4H), 1149, 3.31 (dd, J = 9.9, 4.5 Hz, 1H), 1.63 (d, J = 12.1 Hz, 1036, 953 cm.sup.-1 1H), 1.45 (d, J = 7.2 Hz, 3H), 1.42-1.27 (m, 1H), 1.24-1.08 (m, 1H), 1.03 (d, J = 6.2 Hz, 3H), 1.01-0.91 (m, 1H), 0.88 (t, J = 7.4 Hz, 3H), 0.65 (t, J = 7.4 Hz, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -114.13. 138 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 12.15 (s, film) 3370, calcd for C.sub.23H.sub.30FN.sub.2O.sub.6, 1H), 8.46 (d, J = 8.0 Hz, 1H), 8.01 (d, J = 5.2 Hz, 2964, 449.2082; found, 449.2079 1H), 7.16 (dd, J = 8.5, 6.9 Hz, 1731, 1H), 6.89 (d, J = 5.2 Hz, 1H), 6.57 (dd, 1649, J = 11.1, 2.5 Hz, 1H), 6.51 (td, J = 8.3, 1528, 2.5 Hz, 1H), 5.49-5.40 (m, 1H), 1263, 4.74-4.61 (m, 1H), 3.95 (s, 3H), 3.77 (s, 3H), 1149, 953, 3.06 (dd, J = 9.4, 5.0 Hz, 1H), 731 cm.sup.-1 1.96 (ddq, J = 13.1, 9.1, 6.6 Hz, 1H), 1.42 (d, J = 7.2 Hz, 3H), 1.07 (d, J = 6.3 Hz, 3H), 0.97 (d, J = 6.6 Hz, 3H), 0.66 (d, J = 6.6 Hz, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -114.12. 139 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 12.16 (s, film) 3371, calcd for C.sub.26H.sub.34FN.sub.2O.sub.6, 1H), 8.47 (d, J = 8.1 Hz, 1H), 8.02 (d, J = 5.2 Hz, 2928, 489.2395; found, 489.2401 1H), 7.17 (t, J = 7.7 Hz, 1H), 1731, 6.89 (d, J = 5.2 Hz, 1H), 1649, 6.61-6.46 (m, 2H), 5.44 (p, J = 6.1 Hz, 1H), 1528, 4.69 (p, J = 7.3 Hz, 1H), 3.95 (s, 3H), 1449, 3.76 (s, 3H), 3.12 (d, J = 6.7 Hz, 1H), 1262, 1.84 (d, J = 13.0 Hz, 1H), 1.78-1.48 (m, 1150, 4H), 1.45 (d, J = 7.2 Hz, 3H), 1128, 1.37-1.05 (m, 4H), 1.04 (d, J = 6.3 Hz, 3H), 1035, 953, 1.01-0.86 (m, 1H), 0.75 (qd, J = 12.1, 729 cm.sup.-1 3.6 Hz, 1H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -114.15.

140 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 12.17 (s, film) 3370, calcd for C.sub.25H.sub.32FN.sub.2O.sub.6, 1H), 8.48 (d, J = 8.0 Hz, 1H), 8.02 (d, J = 5.2 Hz, 2944, 475.2239; found, 475.2233 1H), 7.21-7.13 (m, 1H), 1732, 6.89 (d, J = 5.2 Hz, 1H), 6.57 (dd, J = 11.1, 1649, 2.5 Hz, 1H), 6.48 (td, J = 8.3, 2.5 Hz, 1528, 1H), 5.34 (qd, J = 6.2, 3.3 Hz, 1H), 1450, 4.71 (p, J = 7.4 Hz, 1H), 3.95 (s, 3H), 1263, 3.77 (s, 3H), 3.18-3.06 (m, 1H), 1149, 2.21-2.05 (m, 1H), 1.87 (dtd, J = 11.2, 7.1, 1036, 952, 3.5 Hz, 1H), 1.74-1.59 (m, 1H), 731 cm.sup.-1 1.58-1.45 (m, 4H), 1.37 (dddd, J = 26.9, 11.8, 7.7, 3.1 Hz, 1H), 1.28-1.16 (m, 2H), 1.04 (d, J = 6.3 Hz, 3H), 1.02-0.97 (m, 1H), 0.95-0.82 (m, 1H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -114.21. 141 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 12.15 (d, film) 3371, calcd for C.sub.24H.sub.32FN.sub.2O.sub.6, J = 5.4 Hz, 1H), 8.45 (dd, J = 13.9, 8.0 Hz, 2964, 463.2239; found, 463.2234 1H), 8.01 (dd, J = 6.2, 5.2 Hz, 1H), 1731, 7.16 (ddd, J = 8.5, 6.9, 4.0 Hz, 1H), 1649, 6.88 (dd, J = 5.2, 3.9 Hz, 1H), 1451, 6.63-6.47 (m, 2H), 5.50-5.39 (m, 1H), 1263, 4.75-4.59 (m, 1H), 3.95 (d, J = 0.9 Hz, 1149, 3H), 3.77 (s, 3H), 3.29-3.06 (m, 1H), 1036, 952, 1.82-1.66 (m, 1H), 1.49 (dd, J = 12.2, 730 cm.sup.-1 7.1 Hz, 2H), 1.33 (d, J = 7.2 Hz, 1H), 1.20-1.00 (m, 4H), 1.00-0.78 (m, 4H), 0.74-0.63 (m, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -114.11, -114.15. 142 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 12.16 (s, film) 3371, calcd for C.sub.24H.sub.30FN.sub.2O.sub.6, 1H), 8.41 (d, J = 8.0 Hz, 1H), 8.00 (d, J = 5.2 Hz, 2938, 461.2082; found, 461.2073 1H), 7.03 (dd, J = 8.5, 6.8 Hz, 1732, 1H), 6.88 (d, J = 5.2 Hz, 1H), 6.55 (dd, 1649, J = 11.0, 2.5 Hz, 1H), 6.47 (td, J = 8.3, 1529, 2.5 Hz, 1H), 5.24 (q, J = 6.5 Hz, 1H), 1451, 4.61 (p, J = 7.3 Hz, 1H), 3.95 (s, 3H), 1264, 3.79 (s, 3H), 3.25 (s, 1H), 1148, 953, 2.69-2.58 (m, 1H), 2.16-2.04 (m, 1H), 732 cm.sup.-1 1.89-1.57 (m, 4H), 1.51-1.37 (m, 1H), 1.34 (d, J = 7.2 Hz, 3H), 1.13 (d, J = 6.4 Hz, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -114.03. 143 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 12.18 (s, film) 3369, calcd for C.sub.26H.sub.34FN.sub.2O.sub.6, 1H), 8.50 (d, J = 8.1 Hz, 1H), 7.98 (d, J = 5.2 Hz, 2927, 489.2395; found, 489.2399 1H), 7.01 (dd, J = 8.5, 6.8 Hz, 1732, 1H), 6.88 (d, J = 5.2 Hz, 1H), 6.60 (td, 1649, J = 8.2, 2.6 Hz, 1H), 6.54 (dd, J = 11.0, 1528, 2.5 Hz, 1H), 5.46 (s, 1H), 1450, 4.76-4.62 (m, 1H), 3.95 (s, 3H), 3.75 (s, 3H), 1278, 3.39 (s, 1H), 1.80-1.59 (m, 5H), 1263, 1.59-1.46 (m, 4H), 1.17 (qt, J = 13.4, 3.6 Hz, 1035, 954, 1H), 1.08 (d, J = 6.3 Hz, 3H), 731 cm.sup.-1 1.07-0.91 (m, 2H), 0.82 (qt, J = 15.4, 7.4 Hz, 2H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -113.87. 144 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 12.18 (s, film) 3370, calcd for C.sub.25H.sub.32FN.sub.2O.sub.6, 1H), 8.46 (d, J = 8.1 Hz, 1H), 7.96 (d, J = 5.2 Hz, 2943, 475.2239; found, 475.2223 1H), 7.05 (t, J = 7.6 Hz, 1H), 1731, 6.87 (d, J = 5.2 Hz, 1H), 6.59 (td, J = 8.3, 1528, 2.5 Hz, 1H), 6.50 (dd, J = 11.1, 2.5 Hz, 1450, 1H), 5.34 (s, 1H), 4.77-4.59 (m, 1279, 1H), 3.95 (s, 3H), 3.73 (s, 3H), 1263, 3.65-3.13 (m, 1H), 2.30-2.02 (m, 1H), 1148, 1.84 (td, J = 11.6, 10.9, 6.8 Hz, 1H), 1034, 953, 1.69-1.54 (m, 2H), 1.54-1.33 (m, 6H), 731 cm.sup.-1 1.33-1.21 (m, 1H), 1.13 (d, J = 6.4 Hz, 3H), 0.98-0.81 (m, 1H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -114.03. 145 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 12.18 (s, film) 3370, calcd for C.sub.25H.sub.34FN.sub.2O.sub.6, 1H), 8.48 (d, J = 7.9 Hz, 1H), 7.97 (d, J = 5.3 Hz, 2962, 477.2395; found, 477.2389 1H), 7.04 (dd, J = 8.6, 6.8 Hz, 1762, 1H), 6.87 (d, J = 5.2 Hz, 1H), 6.59 (td, 1649, J = 8.2, 2.5 Hz, 1H), 6.52 (dd, J = 11.0, 1528, 2.6 Hz, 1H), 5.50-5.41 (m, 1H), 1451, 4.74-4.64 (m, 1H), 3.95 (s, 3H), 3.74 (s, 3H), 1262, 3.57 (d, J = 10.4 Hz, 1H), 1150, 1.65-1.55 (m, 1H), 1.53 (d, J = 7.2 Hz, 3H), 1034, 954, 1.51-1.23 (m, 2H), 1.17 (dq, J = 14.2, 7.2 Hz, 731 cm.sup.-1 1H), 1.10 (d, J = 6.2 Hz, 3H), 1.01-0.83 (m, 4H), 0.82-0.68 (m, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -113.85. 146 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 12.17 (s, film) 3370, calcd for C.sub.24H.sub.32FN.sub.2O.sub.6, 1H), 8.50 (q, J = 10.0, 8.1 Hz, 1H), 2963, 463.2239; found, 463.2227 7.98 (t, J = 5.5 Hz, 1H), 7.02 (dd, J = 8.4, 1732, 6.8 Hz, 1H), 6.88 (d, J = 5.2 Hz, 1H), 1649, 6.66-6.48 (m, 2H), 5.45 (dd, J = 13.7, 1527, 7.1 Hz, 1H), 4.79-4.63 (m, 1H), 1451, 3.95 (s, 3H), 3.82-3.70 (m, 3H), 3.46 (s, 1278, 1H), 1.87-1.72 (m, 1H), 1.54 (dd, J = 14.3, 1263, 7.1 Hz, 3H), 1.43-1.23 (m, 1H), 1149, 1.09 (dd, J = 11.6, 6.2 Hz, 3H), 1035, 730 cm.sup.-1 0.99-0.80 (m, 4H), 0.80-0.69 (m, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -113.79, -113.87. 147 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 12.18 (s, film) 3371, calcd for C.sub.24H.sub.30FN.sub.2O.sub.6, 1H), 8.47 (d, J = 8.1 Hz, 1H), 7.98 (d, J = 5.2 Hz, 2939, 461.2082; found, 461.2060 1H), 6.97 (dd, J = 8.5, 6.7 Hz, 1733, 1H), 6.87 (d, J = 5.2 Hz, 1H), 1529, 6.61-6.50 (m, 2H), 5.19 (s, 1H), 1280, 4.74-4.60 (m, 1H), 3.95 (s, 3H), 3.78 (s, 3H), 1264, 3.34 (s, 1H), 2.79 (hept, J = 8.8, 7.9 Hz, 1H), 11748, 954 cm.sup.-1 2.20-2.06 (m, 1H), 2.00-1.83 (m, 1H), 1.83-1.71 (m, 1H), 1.71-1.59 (m, 2H), 1.51 (dd, J = 7.2, 2.7 Hz, 3H), 1.42 (qd, J = 9.6, 1.7 Hz, 1H), 1.10 (d, J = 6.4 Hz, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -113.83. 148 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. film) 3371, calcd for C.sub.23H.sub.30FN.sub.2O.sub.6, 12.18-12.16 (m, 1H), 8.50 (d, J = 7.9 Hz, 1H), 2961, 449.2082; found, 449.2063 7.98 (d, J = 5.2 Hz, 1H), 7.01 (dd, J = 8.5, 1732, 6.7 Hz, 1H), 6.88 (d, J = 5.2 Hz, 1528, 1H), 6.61 (td, J = 8.3, 2.6 Hz, 1H), 1280, 6.55 (dd, J = 11.0, 2.5 Hz, 1H), 5.44 (d, J = 7.5 Hz, 1262, 1H), 4.76-4.64 (m, 1H), 1149, 4.12 (q, J = 7.2 Hz, 0H), 3.95 (s, 3H), 1034, 953, 3.75 (s, 3H), 3.34 (s, 1H), 2.14-2.02 (m, 730 cm.sup.-1 1H), 1.54 (d, J = 7.2 Hz, 3H), 1.09 (d, J = 6.3 Hz, 3H), 0.85 (d, J = 6.7 Hz, 3H), 0.73 (d, J = 6.8 Hz, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -113.80. 149 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 12.15 (d, film) 2937, calcd for C.sub.25H.sub.33F.sub.4N.sub.2O.sub.5, J = 0.6 Hz, 1H), 8.40 (d, J = 8.0 Hz, 1732, 441.2384; found, 441.2378 1H), 7.99 (d, J = 5.2 Hz, 1H), 7.00 (d, J = 7.8 Hz, 1689, 1H), 6.93-6.83 (m, 3H), 1527, 5.24-5.12 (m, 1H), 4.65-4.51 (m, 1439, 910, 1H), 3.94 (s, 3H), 3.04 (dd, J = 10.5, 800, 729 cm.sup.-1 6.5 Hz, 1H), 2.75-2.60 (m, 1H), 2.31 (s, 3H), 2.24 (s, 3H), 2.21-2.09 (m, 1H), 1.88-1.61 (m, 4H), 1.41 (pd, J = 10.1, 3.5 Hz, 1H), 1.24 (d, J = 7.2 Hz, 3H), 1.19 (d, J = 6.3 Hz, 3H). 150 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 12.14 (s, film) 3370, calcd for C.sub.22H.sub.28ClN.sub.2O.sub.5, 1H), 8.44 (d, J = 8.0 Hz, 1H), 8.00 (d, J = 5.2 Hz, 2962, 435.1681; found, 435.168 1H), 7.22 (d, J = 8.4 Hz, 2H), 1735, 7.02 (d, J = 8.4 Hz, 2H), 6.89 (d, J = 5.2 Hz, 1649, 1H), 5.45-5.34 (m, 1H), 1529, 4.76-4.61 (m, 1H), 3.96 (s, 3H), 2.69 (t, J = 7.6 Hz, 1481, 1H), 2.13-2.00 (m, 1H), 1264, 1.54 (d, J = 6.6 Hz, 3H), 1.10 (d, J = 6.3 Hz, 1152, 3H), 0.88 (d, J = 6.7 Hz, 3H), 0.74 (d, J = 6.7 Hz, 1052, 826, 3H). 801 cm.sup.-1 .sup.13C NMR (126 MHz, CDCl.sub.3) .delta. 171.59, 168.72, 155.41, 148.78, 140.51, 137.11, 132.47, 130.99, 130.44, 128.13, 109.49, 77.21, 72.62, 56.11, 56.01, 48.18, 28.32, 21.17, 18.86, 18.31, 17.31. 151 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 12.14 (s, film) 3370, calcd for C.sub.23H.sub.30FN.sub.2O.sub.5, 1H), 8.48 (d, J = 7.9 Hz, 1H), 8.00 (d, J = 5.2 Hz, 2961, 434.2165; found, 434.2169 1H), 7.06 (t, J = 7.9 Hz, 1H), 1734, 6.88 (d, J = 5.2 Hz, 1H), 1649, 6.81-6.71 (m, 2H), 5.43-5.32 (m, 1H), 1576, 4.73-4.63 (m, 1H), 3.95 (s, 3H), 2.67 (t, 1H), 1528, 2.24 (s, 3H), 2.12-1.99 (m, 1H), 1481, 1.55 (d, 3H), 1.11 (d, J = 6.3 Hz, 3H), 1280, 0.87 (d, J = 6.7 Hz, 3H), 0.76 (d, J = 6.8 Hz, 1262, 800 cm.sup.-1 3H). .sup.13C NMR (126 MHz, CDCl.sub.3) .delta. 171.66, 168.71, 161.91, 159.97, 155.38, 148.76, 140.49, 138.29, 138.23, 130.83, 130.79, 130.48, 125.23, 125.20, 123.02, 122.88, 116.15, 115.98, 109.44, 77.22, 72.79, 56.09, 56.07, 48.17, 34.67, 31.59, 28.33, 25.28, 22.66, 21.22, 20.71, 18.75, 18.34, 17.51, 14.20, 14.17, 14.13. 152 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 12.12 (s, film) 2963, calcd for 1H), 8.43 (d, J = 8.1 Hz, 1H), 8.00 (d, J = 5.2 Hz, 1736, C.sub.22H.sub.27F.sub.2N.sub.2O.sub.5, 438.1915; 1H), 7.09-6.98 (m, 1H), 1649, found, 438.1921 6.95-6.86 (m, 2H), 6.84-6.75 (m, 1517, 1H), 5.43-5.33 (m, 1H), 1481, 4.74-4.60 (m, 1H), 3.96 (s, 3H), 2.68 (t, J = 7.6 Hz, 1281, 1H), 2.11-2.00 (m, 1H), 1.53 (d, 1264, 3H), 1.12 (d, J = 6.3 Hz, 3H), 0.89 (d, J = 6.7 Hz, 1212, 3H), 0.75 (d, J = 6.7 Hz, 3H). 1053, 801 cm.sup.-1 .sup.13C NMR (126 MHz, CDCl.sub.3) .delta. 171.54, 168.73, 155.41, 148.78, 140.52, 130.40, 118.11, 109.49, 77.21, 72.45, 56.11, 55.86, 48.16, 28.43, 21.11, 18.94, 18.28, 17.15. 153 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 12.15 (d, film) 2962, calcd for C.sub.23H.sub.31FN.sub.2O.sub.5, J = 0.6 Hz, 1H), 8.49 (d, J = 7.9 Hz, 1734, 433.2133; found, 433.2129 1H), 8.00 (d, J = 5.2 Hz, 1H), 1715, 6.93-6.82 (m, 4H), 5.38 (dq, J = 8.6, 6.3 Hz, 1530, 1H), 4.73-4.63 (m, 1H), 3.95 (s, 3H), 1481, 2.66 (dd, J = 8.6, 6.6 Hz, 1H), 2.24 (d, J = 1.9 Hz, 1282, 3H), 2.06 (hept, J = 6.8 Hz, 1264, 1H), 1.55 (d, J = 7.2 Hz, 3H), 1.10 (d, J = 6.3 Hz, 1244, 3H), 0.85 (d, J = 6.7 Hz, 3H), 1220, 801 cm.sup.-1 0.75 (d, J = 6.8 Hz, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 171.65, 168.73, 160.27 (d, J = 243.5 Hz), 155.40, 148.79, 140.47, 133.95 (d, J = 3.8 Hz), 132.52 (d, J = 4.9 Hz), 130.50, 128.31 (d, J = 7.7 Hz), 124.11 (d, J = 17.0 Hz), 114.39 (d, J = 22.0 Hz), 109.48, 72.95, 56.07, 55.82, 48.20, 28.32, 21.25, 18.68, 18.29, 17.62, 14.61 (d, J = 3.5 Hz). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -120.75. 154 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 12.16 (d, film) 3367, calcd for C.sub.23H.sub.30FN.sub.2O.sub.6, J = 0.6 Hz, 1H), 8.50 (d, J = 7.9 Hz, 2963, 449.2082; found, 449.2076 1H), 7.99 (d, J = 5.2 Hz, 1H), 7.03 (t, J = 8.5 Hz, 1734, 1H), 6.91-6.84 (m, 1H), 1649, 6.66 (ddd, J = 8.6, 2.6, 0.8 Hz, 1H), 1530, 6.57 (dd, J = 12.0, 2.6 Hz, 1H), 1508, 5.44 (dqd, J = 7.6, 6.3, 1.2 Hz, 1H), 1282, 4.75-4.63 (m, 1H), 3.94 (s, 3H), 3.78 (s, 3H), 1264, 3.10 (t, J = 7.7 Hz, 1H), 2.09 (tt, J = 13.5, 1149, 801, 6.6 Hz, 1H), 1.55 (d, J = 7.2 Hz, 731 cm.sup.-1 3H), 1.12 (d, J = 6.3 Hz, 3H), 0.94-0.87 (m, 3H), 0.76 (d, J = 6.7 Hz, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 171.68, 168.74, 162.09 (d, J = 244.2 Hz), 159.37 (d, J = 11.4 Hz), 155.38, 148.78, 140.47, 130.67 (d, J = 6.6 Hz), 130.56, 117.46 (d, J = 15.4 Hz), 109.59 (d, J = 3.0 Hz),

109.46, 101.41 (d, J = 27.9 Hz), 72.76, 56.07, 55.44, 48.21, 47.95, 28.41, 21.06, 19.09, 18.15, 17.30. .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -113.05. 155 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 12.15 (d, film) 3367, calcd for C.sub.23H.sub.30FN.sub.2O.sub.6, J = 0.6 Hz, 1H), 8.48 (d, J = 7.9 Hz, 2962, 449.2082; found, 449.2082 1H), 8.00 (d, J = 5.2 Hz, 1H), 1715, 6.90-6.77 (m, 4H), 5.36 (dq, J = 8.4, 6.3 Hz, 1518, 1H), 4.73-4.64 (m, 1H), 3.95 (s, 3H), 1273, 3.87 (s, 3H), 2.68-2.60 (m, 1H), 1222, 801 cm.sup.-1 2.05 (h, J = 6.7 Hz, 1H), 1.55 (d, J = 7.2 Hz, 3H), 1.11 (d, J = 6.3 Hz, 3H), 0.87 (d, J = 6.7 Hz, 3H), 0.76 (d, J = 6.7 Hz, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 171.63, 168.76, 155.40, 151.94 (d, J = 245.1 Hz), 148.79, 146.29 (d, J = 10.7 Hz), 140.51, 131.69 (d, J = 5.6 Hz), 130.50, 125.45 (d, J = 3.5 Hz), 117.10 (d, J = 18.2 Hz), 112.94 (d, J = 2.2 Hz), 109.50, 72.80, 56.21, 56.08, 55.73, 48.21, 28.40, 21.21, 18.79, 18.30, 17.45. .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -135.65. 156 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 12.19 (d, film) 3367, calcd for C.sub.24H.sub.33N.sub.2O.sub.6, J = 0.6 Hz, 1H), 8.53 (d, J = 7.9 Hz, 2960, 445.2333; found, 445.2332 1H), 7.98 (d, J = 5.2 Hz, 1H), 6.94 (d, J = 7.7 Hz, 1732, 1H), 6.87 (d, J = 5.1 Hz, 1H), 1649, 6.71 (dt, J = 7.7, 1.1 Hz, 1H), 6.66 (d, J = 1.5 Hz, 1528, 1H), 5.51-5.35 (m, 1H), 1262, 4.75-4.64 (m, 1H), 3.94 (s, 3H), 1041, 800, 3.76 (s, 3H), 3.34 (s, 1H), 2.32 (s, 3H), 730 cm.sup.-1 2.09 (h, J = 6.7 Hz, 1H), 1.55 (d, J = 7.2 Hz, 3H), 1.09 (d, J = 6.2 Hz, 3H), 0.84 (d, J = 6.7 Hz, 3H), 0.74 (d, J = 6.8 Hz, 3H). 157 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 12.15 (d, film) 2960, calcd for C.sub.24H.sub.33N.sub.2O.sub.6, J = 0.6 Hz, 1H), 8.51 (d, J = 7.9 Hz, 1715, 445.2333; found, 445.2328 1H), 7.99 (d, J = 5.2 Hz, 1H), 7.00 (dd, 1529, J = 8.1, 0.8 Hz, 1H), 6.90-6.85 (m, 1281, 1H), 6.70 (d, J = 8.2 Hz, 2H), 5.37 (dq, 1222, J = 9.2, 6.2 Hz, 1H), 4.76-4.66 (m, 1048, 801, 1H), 3.95 (s, 3H), 3.78 (s, 3H), 732 cm.sup.-1 3.07 (dd, J = 9.2, 6.1 Hz, 1H), 2.29 (s, 3H), 2.11 (dq, J = 13.4, 6.8 Hz, 1H), 1.56 (d, J = 7.1 Hz, 3H), 1.07 (d, J = 6.2 Hz, 3H), 0.84 (d, J = 6.8 Hz, 3H), 0.79 (d, J = 6.8 Hz, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 171.80, 168.71, 157.59, 155.39, 148.79, 140.47, 138.86, 130.54, 129.90, 128.80, 115.92, 110.88, 109.47, 74.41, 56.08, 55.04, 48.26, 29.71, 29.29, 21.08, 20.96, 18.76, 18.27, 18.23. 158 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 12.18 (d, film) 3370, calcd for C.sub.23H.sub.31N.sub.2O.sub.6, J = 0.6 Hz, 1H), 8.52 (d, J = 7.9 Hz, 2961, 431.2177; found, 431.2155 1H), 7.99 (d, J = 5.2 Hz, 1H), 1732, 7.22-6.77 (m, 5H), 5.55-5.36 (m, 1H), 1649, 4.76-4.59 (m, 1H), 3.94 (s, 3H), 3.77 (s, 1528, 3H), 3.55-3.22 (m, 1H), 1241, 2.18-2.05 (m, 1H), 1.55 (d, J = 7.2 Hz, 3H), 1050, 755, 1.09 (d, J = 6.3 Hz, 3H), 0.85 (d, J = 6.8 Hz, 731 cm.sup.-1 3H), 0.74 (d, J = 6.8 Hz, 3H). 159 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 12.19 (s, film) 3369, calcd for C.sub.24H.sub.33N.sub.2O.sub.7, 1H), 8.53 (d, J = 7.9 Hz, 1H), 7.99 (d, J = 5.2 Hz, 2960, 461.2282; found, 461.2266 1H), 6.96 (d, J = 8.2 Hz, 1H), 1732, 6.87 (d, J = 5.3 Hz, 1H), 1649, 6.52-6.38 (m, 2H), 5.43 (s, 1H), 4.77-4.60 (m, 1528, 1H), 3.95 (s, 3H), 3.79 (s, 3H), 3.75 (s, 1262, 3H), 3.41-3.14 (m, 1H), 2.07 (dq, J = 13.4, 1207, 6.7 Hz, 1H), 1.55 (d, J = 7.1 Hz, 1156, 3H), 1.09 (d, J = 6.2 Hz, 3H), 0.83 (d, J = 6.7 Hz, 1042, 730 cm.sup.-1 3H), 0.73 (d, J = 6.8 Hz, 3H). 160 HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (300 MHz, CDCl.sub.3) .delta. 8.54 (d, calcd for C.sub.24H.sub.31N.sub.2O.sub.6, J = 8.0 Hz, 1H), 8.34 (d, J = 5.4 Hz, 443.2182; found, 443.2187 1H), 7.33-7.10 (m, 5H), 7.00 (d, J = 5.4 Hz, 1H), 5.56-5.34 (m, 1H), 4.79-4.54 (m, 1H), 3.89 (s, 3H), 2.39 (s, 3H), 2.34 (dd, J = 8.7, 5.4 Hz, 1H), 2.14-1.95 (m, 1H), 1.29 (d, J = 7.2 Hz, 3H), 1.09 (d, J = 6.2 Hz, 3H), 0.95 (d, J = 6.6 Hz, 3H), 0.71 (d, J = 6.7 Hz, 3H). .sup.13C NMR (75 MHz, CDCl.sub.3) .delta. 172.24, 168.91, 162.34, 159.46, 146.68, 141.49, 139.86, 137.49, 129.63, 127.90, 126.47, 109.79, 72.07, 58.01, 56.30, 56.26, 48.08, 29.24, 21.24, 20.74, 20.42, 18.92, 18.49. 161 HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (300 MHz, CDCl.sub.3) .delta. 8.58 (d, calcd for C.sub.26H.sub.33N.sub.2O.sub.6, J = 8.0 Hz, 1H), 8.34 (d, J = 5.4 Hz, 469.2338; found, 469.2345 1H), 7.33-7.09 (m, 5H), 7.01 (d, J = 5.5 Hz, 1H), 5.35 (qd, J = 6.3, 3.8 Hz, 1H), 4.83-4.65 (m, 1H), 3.89 (s, 3H), 2.43-2.38 (m, 1H), 2.40 (s, 3H), 2.29-2.14 (m, 1H), 1.93-1.78 (m, 1H), 1.70-1.50 (m, 3H), 1.45 (d, J = 7.2 Hz, 3H), 1.41-1.26 (m, 2H), 1.24-1.14 (m, 1H), 1.06 (d, J = 6.3 Hz, 3H), 0.95-0.77 (m, 1H). .sup.13C NMR (75 MHz, CDCl.sub.3) .delta. 172.20, 168.90, 162.36, 159.49, 146.67, 141.47, 140.72, 137.53, 129.49, 127.92, 126.44, 109.82, 73.34, 56.66, 56.31, 56.27, 48.20, 42.11, 31.70, 31.45, 25.11, 24.51, 20.74, 18.72. 162 HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (300 MHz, CDCl.sub.3) .delta. 8.36 (d, calcd for C.sub.25H.sub.33N.sub.2O.sub.7, J = 7.9 Hz, 1H), 8.29 (d, J = 5.3 Hz, 473.2288; found, 473.2294 1H), 7.28-7.11 (m, 5H), 6.96 (d, J = 5.4 Hz, 1H), 5.83-5.67 (m, 2H), 5.60-5.35 (m, 1H), 4.83-4.55 (m, 1H), 3.90 (s, 3H), 2.37 (dd, J = 8.5, 5.6 Hz, 1H), 2.12-2.00 (m, 1H), 2.06 (s, 3zH), 1.29 (d, J = 7.2 Hz, 3H), 1.12 (d, J = 6.2 Hz, 3H), 0.95 (d, J = 6.6 Hz, 3H), 0.72 (d, J = 6.7 Hz, 3H). .sup.13C NMR (75 MHz, CDCl.sub.3) .delta. 172.35, 170.26, 162.90, 160.29, 145.71, 143.99, 142.47, 139.82, 129.61, 127.90, 126.46, 109.58, 89.54, 72.07, 57.98, 56.20, 56.17, 48.26, 29.22, 21.27, 20.88, 20.85, 20.28, 18.93, 18.32. 163 HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (300 MHz, CDCl.sub.3) .delta. 8.41 (d, calcd for C.sub.27H.sub.35N.sub.2O.sub.7, J = 7.8 Hz, 1H), 8.30 (d, J = 5.3 Hz, 499.2444; found, 499.2449 1H), 7.30-7.15 (m, 5H), 6.97 (d, J = 5.4 Hz, 1H), 5.87-5.65 (m, 2H), 5.36 (qd, J = 6.4, 3.9 Hz, 1H), 4.94-4.63 (m, 1H), 3.91 (s, 3H), 2.42 (dd, J = 10.3, 3.9 Hz, 1H), 2.34-2.14 (m, 1H), 2.07 (s, 3H), 1.96-1.79 (m, 1H), 1.75-1.49 (m, 3H), 1.46 (d, J = 7.1 Hz, 3H), 1.45-1.28 (m, 2H), 1.27-1.16 (m, 1H), 1.08 (d, J = 6.3 Hz, 3H), 0.95-0.73 (m, 1H). .sup.13C NMR (75 MHz, CDCl.sub.3) .delta. 172.32, 170.28, 162.93, 160.32, 145.71, 144.05, 142.45, 140.73, 129.48, 127.94, 126.44, 109.60, 89.58, 73.34, 56.64, 56.22, 56.18, 48.39, 42.14, 31.64, 31.45, 25.10, 24.50, 20.89, 20.86, 18.76, 18.57. 164 HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (300 MHz, CDCl.sub.3) .delta. 8.38 (d, calcd for C.sub.25H.sub.33N.sub.2O.sub.7, J = 7.7 Hz, 1H), 8.29 (d, J = 5.4 Hz, 473.2288; found, 473.2279 1H), 7.30-7.19 (m, 3H), 7.17-7.06 (m, 2H), 6.96 (d, J = 5.4 Hz, 1H), 5.75 (s, 2H), 5.43 (dq, J = 8.7, 6.2 Hz, 1H), 4.90-4.52 (m, 1H), 3.92 (s, 3H), 2.72 (dd, J = 8.8, 6.4 Hz, 1H), 2.19-2.09 (m, 1H), 2.08 (s, 3H), 1.53 (d, J = 7.2 Hz, 3H), 1.10 (d, J = 6.3 Hz, 3H), 0.86 (d, J = 6.7 Hz, 3H), 0.77 (d, J = 6.8 Hz, 3H). .sup.13C NMR (75 MHz, CDCl.sub.3) .delta. 172.39, 170.32, 162.98, 160.29, 145.73, 144.03, 142.52, 138.62, 129.81, 127.90, 126.61, 109.56, 89.60, 72.72, 56.61, 56.22, 56.18, 48.41, 28.24, 21.34, 20.89, 18.54, 17.86. 165 HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.54 (d, calcd for C.sub.24H.sub.31N.sub.2O.sub.6, J = 8.1 Hz, 1H), 8.33 (d, J = 5.4 Hz, 443.2182; found, 443.2177 1H), 7.30-7.17 (m, 3H), 7.14-7.05 (m, 2H), 7.00 (d, J = 5.4 Hz, 1H), 5.42 (dq, J = 8.7, 6.3 Hz, 1H), 4.69 (p, J = 7.3 Hz, 1H), 3.90 (s, 3H), 2.71 (dd, J = 8.6, 6.5 Hz, 1H), 2.39 (s, 3H), 2.17-2.03 (m, 1H), 1.50 (d, J = 7.2 Hz, 3H), 1.09 (d, J = 6.3 Hz, 3H), 0.86 (d, J = 6.8 Hz, 3H), 0.76 (d, J = 6.7 Hz, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 172.22, 168.83, 162.38, 159.48, 146.63, 141.63, 138.69, 137.54, 129.79, 127.88, 126.58, 109.74, 72.74, 56.64, 56.26, 48.21, 28.26, 21.32, 20.72, 18.64, 18.62, 17.80. 166 HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.60 (d, calcd for C.sub.25H.sub.31N.sub.2O.sub.6, J = 8.0 Hz, 1H), 8.37 (d, J = 5.4 Hz, 455.2177; found, 455.2169 1H), 7.18-7.10 (m, 4H), 7.05 (d, J = 5.5 Hz, 1H), 5.50-5.31 (m, 1H), 4.91-4.66 (m, 1H), 3.94 (s, 3H), 2.44 (s, 3H), 2.36 (s, 3H), 2.03 (dd, J = 10.0, 7.0 Hz, 1H), 1.52 (d, J = 7.1 Hz, 3H), 1.20 (d, J = 6.4 Hz, 3H), 1.19-1.08 (m, 1H), 0.76-0.62 (m, 1H), 0.51-0.34 (m, 2H), 0.05--0.08 (m, 1H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 172.21, 168.85, 162.33, 159.48, 146.64, 141.64, 138.58, 137.52, 136.08, 128.92, 128.29, 109.76, 75.92, 56.27, 55.25, 48.18, 21.01, 20.73, 18.68, 18.12, 13.03, 6.93, 2.87. 167 HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.43 (d, calcd for C.sub.26H.sub.33N.sub.2O.sub.7, J = 7.9 Hz, 1H), 8.33 (d, J = 5.3 Hz, 485.2283; found, 485.2281 1H), 7.18-7.10 (m, 4H), 7.01 (d, J = 5.4 Hz, 1H), 5.80 (s, 2H), 5.46-5.25 (m, 1H), 4.90-4.72 (m, 1H), 3.96 (s, 3H), 2.37 (s, 3H), 2.12 (s, 3H), 2.05 (dd, J = 10.0, 7.0 Hz, 1H), 1.55 (d, J = 7.1 Hz, 3H), 1.22 (d, J = 6.3 Hz, 3H), 1.20-1.09 (m, 1H), 0.75-0.65 (m, 1H), 0.51-0.37 (m, 2H), 0.08--0.06 (m, 1H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 172.32, 170.20, 162.91, 160.30, 145.68, 143.99, 142.61, 138.58, 136.07, 128.91, 128.28, 109.57, 89.55, 75.89, 56.17, 55.24, 48.37, 21.00, 20.83, 18.53, 18.14, 13.01, 6.94, 2.87. 168 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.55 (d, film) 3380, calcd for C.sub.25H.sub.33N.sub.2O.sub.6, J = 8.0 Hz, 1H), 8.34 (d, J = 5.4 Hz, 2961, 457.2333; found, 457.2328 1H), 7.06 (t, J = 6.4 Hz, 2H), 1771, 7.03-6.94 (m, 3H), 5.40 (dq, J = 8.7, 6.3 Hz, 1732, 1H), 4.74-4.62 (m, 1H), 3.91 (s, 3H), 1676, 2.67 (dd, J = 8.8, 6.3 Hz, 1H), 2.40 (s, 1508, 3H), 2.32 (s, 3H), 2.14-2.05 (m, 1H), 1199, 1.50 (d, J = 7.2 Hz, 3H), 1.08 (d, J = 6.3 Hz, 1175, 908, 3H), 0.85 (d, J = 6.7 Hz, 3H), 823, 802, 0.75 (d, J = 6.7 Hz, 3H). 731 cm.sup.-1 .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 172.28, 168.90, 162.39, 159.49, 146.65, 141.67, 137.55, 136.06, 135.51, 129.68, 128.62, 109.73, 72.85, 56.29, 56.23, 48.23, 28.21, 21.36, 21.01, 20.75, 18.69, 18.56, 17.85. 169 HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3)

.delta. 8.51 (d, calcd for C.sub.24H.sub.30FN.sub.2O.sub.6, J = 7.9 Hz, 1H), 8.39-8.28 (m, 1H), 461.2083; found, 461.2082 7.12-6.89 (m, 5H), 5.50-5.32 (m, 1H), 4.78-4.60 (m, 1H), 3.91 (s, 3H), 2.77-2.64 (m, 1H), 2.41 (s, 3H), 2.14-2.02 (m, 1H), 1.54-1.35 (m, 3H), 1.12-0.97 (m, 3H), 0.94-0.83 (m, 3H), 0.79-0.68 (m, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -116.57, -116.61. 170 HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.51 (d, calcd for C.sub.24H.sub.28FN.sub.2O.sub.6, J = 8.3 Hz, 1H), 8.32 (d, J = 5.4 Hz, 459.1926; found, 459.1923 1H), 7.22-7.10 (m, 2H), 7.09-6.86 (m, 3H), 5.39-5.19 (m, 1H), 4.71 (dq, J = 8.2, 7.2 Hz, 1H), 3.90 (s, 3H), 2.40 (s, 3H), 2.02 (dd, J = 10.1, 6.5 Hz, 1H), 1.46 (d, J = 7.2 Hz, 3H), 1.17 (d, J = 6.4 Hz, 3H), 1.12-1.03 (m, 1H), 0.73-0.62 (m, 1H), 0.47-0.31 (m, 2H), -0.01--0.14 (m, 1H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -116.54. 171 HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.35 (d, calcd for C.sub.25H.sub.30FN.sub.2O.sub.7, J = 8.0 Hz, 1H), 8.31-8.19 (m, 1H), 489.2032; found, 489.2027 7.23-7.14 (m, 2H), 7.03-6.82 (m, 3H), 5.75 (s, 2H), 5.36-5.19 (m, 1H), 4.82-4.65 (m, 1H), 3.92 (s, 3H), 2.07 (s, 3H), 2.03 (dd, J = 10.2, 6.5 Hz, 1H), 1.48 (d, J = 7.2 Hz, 3H), 1.18 (d, J = 6.4 Hz, 3H), 1.15-1.06 (m, 1H), 0.75-0.63 (m, 1H), 0.48-0.33 (m, 2H), -0.03--0.12 (m, 1H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -116.54. 172 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (300 MHz, CDCl.sub.3) .delta. 8.57 (d, film) 3382, calcd for C.sub.26H.sub.35N.sub.2O.sub.6, J = 7.3 Hz, 1H), 8.33 (d, J = 5.4 Hz, 2962, 471.2495; found, 471.2494 1H), 7.33-7.06 (m, 5H), 7.01 (d, J = 5.5 Hz, 2933, 1H), 5.52-5.36 (m, 1H), 2875, 4.70 (p, J = 7.1 Hz, 1H), 3.90 (s, 3H), 1771, 2.96 (dd, J = 8.6, 6.3 Hz, 1H), 2.40 (s, 3H), 1732, 1.50 (d, J = 7.2 Hz, 3H), 1676, 1.46-1.22 (m, 3H), 1.10 (d, J = 6.2 Hz, 3H), 1505, 0.99-0.82 (m, 5H), 0.78 (t, J = 7.2 Hz, 1309, 3H). 1193, 1174, 1040, 826, 734, 703 cm.sup.-1. 173 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (300 MHz, CDCl.sub.3) .delta. 8.53 (d, film) 3381, calcd for C.sub.26H.sub.33N.sub.2O.sub.6, J = 7.8 Hz, 1H), 8.32 (d, J = 4.6 Hz, 2950, 469.2338; found, 469.2342 1H), 7.33-7.06 (m, 5H), 7.01 (d, J = 5.5 Hz, 1771, 1H), 5.48-5.16 (m, 1H), 1732, 4.85-4.55 (m, 1H), 3.89 (s, 3H), 2.78 (dd, J = 10.0, 1676, 5.9 Hz, 1H), 2.39 (s, 3H), 1505, 1.98-1.80 (m, 1H), 1.73-1.19 (m, 11H), 1309, 1.11 (d, J = 6.5 Hz, 3H). 1195, 1174, 1038, 826, 802, 734, 702 cm.sup.-1. 174 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (300 MHz, CDCl.sub.3) .delta. 8.40 (d, film) 3380, calcd for C.sub.27H.sub.37N.sub.2O.sub.7, J = 7.9 Hz, 1H), 8.29 (d, J = 5.4 Hz, 2962, 501.2601; found, 501.2606 1H), 7.34-7.06 (m, 5H), 6.96 (d, J = 5.4 Hz, 2933, 1H), 5.75 (s, 2H), 1734, 5.57-5.35 (m, 1H), 4.81-4.54 (m, 1H), 3.91 (s, 1676, 3H), 2.97 (dd, J = 8.6, 6.3 Hz, 1H), 1502, 2.07 (s, 3H), 1.53 (d, J = 7.2 Hz, 3H), 1452, 1.49-1.34 (m, 3H), 1.11 (d, J = 6.3 Hz, 3H), 1310, 0.95 (t, J = 7.3 Hz, 3H), 0.91-0.82 (m, 1200, 2H), 0.78 (t, J = 7.2 Hz, 3H). 1041, 1002, 967, 829, 735, 704 cm.sup.-1. 175 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (300 MHz, CDCl.sub.3) .delta. 8.36 (d, film) 3382, calcd for C.sub.27H.sub.35N.sub.2O.sub.7, J = 7.8 Hz, 1H), 8.28 (d, J = 5.2 Hz, 2948, 499.2444; found, 499.2447 1H), 7.32-7.02 (m, 5H), 6.97 (dd, J = 5.4, 2869, 2.6 Hz, 1H), 5.75 (s, 2H), 1733, 5.45-5.17 (m, 1H), 4.85-4.40 (m, 1H), 1501, 3.91 (s, 3H), 2.79 (dd, J = 10.0, 5.9 Hz, 1H), 1437, 2.07 (s, 3H), 2.02-1.77 (m, 2H), 1310, 1.67-1.19 (m, 7H), 1.13-0.86 (m, 6H). 1200, 1040, 1002, 967, 829, 734, 703 cm.sup.-1. 176 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3, major) .delta. film) 2950, calcd for C.sub.26H.sub.33N.sub.2O.sub.5S, 9.94 (d, J = 6.5 Hz, 1H), 8.33 (d, J = 5.5 Hz, 1769, 485.2105; found, 485.2171 1H), 7.26-7.20 (m, 3H), 1732, 7.14-7.10 (m, 2H), 7.00 (d, J = 5.5 Hz, 1H), 1192, 5.38-5.31 (m, 1H), 5.17-5.08 (m, 1175, 730 cm.sup.-1 1H), 3.91 (s, 3H), 2.79 (dd, J = 9.9, 6.0 Hz, 1H), 2.36 (s, 3H), 2.28-2.12 (m, 1H), 1.98-1.82 (m, 2H), 1.57 (d, J = 7.2 Hz, 3H), 1.53-1.36 (m, 4H), 1.34-1.20 (m, 2H), 1.13 (d, J = 6.5 Hz, 3H). 177 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 9.98 (d, film) 2950, calcd for C.sub.26H.sub.32N.sub.2O.sub.5S, J = 7.3 Hz, 1H), 8.35 (d, J = 5.4 Hz, 2868, 507.1924; found, 507.1920 1H), 7.25-7.13 (m, 5H), 7.01 (d, J = 5.5 Hz, 1770, 1H), 5.39 (qd, J = 6.3, 4.1 Hz, 1731, 1H), 5.16 (p, J = 7.2 Hz, 1H), 3.91 (s, 1585, 3H), 2.42 (dd, J = 10.3, 4.0 Hz, 1H), 1496, 2.35 (s, 3H), 2.28-2.19 (m, 1H), 1438, 1.93-1.83 (m, 1H), 1.68-1.59 (m, 1H), 1365, 1.52 (d, J = 7.2 Hz, 3H), 1.50-1.31 (m, 4H), 1311, 1.20 (dq, J = 12.5, 9.1 Hz, 1H), 1.08 (d, 1278, J = 6.4 Hz, 3H), 0.97-0.90 (m, 1H). 1193, 1175, 1131, 1102, 1040, 1010, 909, 847, 824, 759, 703 cm.sup.-1 178 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.52 (s, film) 3384, calcd for C.sub.25H.sub.31FN.sub.2NaO.sub.6, 1H), 8.35 (d, J = 5.4 Hz, 1H), 2968, 497.2058; found, 497.2056 7.31-7.22 (m, 1H), 7.02 (d, J = 5.5 Hz, 1H), 1772, 6.84 (dd, J = 9.9, 2.9 Hz, 1H), 6.76 (td, 1733, J = 8.5, 2.8 Hz, 1H), 5.48-5.36 (m, 1677, 1H), 4.76-4.62 (m, 1H), 3.91 (s, 3H), 1499, 2.67 (dd, J = 9.4, 4.8 Hz, 1H), 2.39 (s, 1176, 825, 3H), 2.27 (s, 3H), 2.01 (dp, J = 9.2, 6.6 Hz, 734 cm.sup.-1 1H), 1.39 (d, J = 7.2 Hz, 3H), 1.05 (d, J = 6.3 Hz, 3H), 0.99 (d, J = 6.6 Hz, 3H), 0.68 (d, J = 6.7 Hz, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.72. 179 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.54 (d, film) 3384, calcd for C.sub.27H.sub.35FN.sub.2NaO.sub.6, J = 7.6 Hz, 1H), 8.35 (d, J = 5.5 Hz, 2963, 525.2371; found, 525.2364 1H), 7.30 (dd, J = 8.8, 6.2 Hz, 1H), 1771, 7.02 (dd, J = 5.5, 2.6 Hz, 1H), 6.83 (dd, J = 9.9, 1732, 2.9 Hz, 1H), 6.75 (td, J = 8.6, 2.9 Hz, 1676, 1H), 5.38 (qd, J = 6.3, 4.0 Hz, 1H), 1498, 4.79-4.65 (m, 1H), 3.91 (s, 3H), 1174, 825, 2.90 (dd, J = 10.1, 4.2 Hz, 1H), 2.39 (s, 3H), 731 cm.sup.-1 2.27 (d, J = 3.5 Hz, 3H), 1.82-1.67 (m, 1H), 1.58-1.28 (m, 4H), 1.26 (s, 1H), 1.19-1.05 (m, 1H), 0.99 (dd, J = 10.0, 6.3 Hz, 3H), 0.94-0.81 (m, 4H), 0.72-0.63 (m, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.69. 180 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.54 (d, film) 3384, calcd for C.sub.27H.sub.33FN.sub.2NaO.sub.6, J = 8.0 Hz, 1H), 8.35 (d, J = 5.4 Hz, 2950, 523.2215; found, 523.2210 1H), 7.31-7.22 (m, 1H), 7.02 (d, J = 5.4 Hz, 1771, 1H), 6.83 (dd, J = 9.9, 2.8 Hz, 1731, 1H), 6.73 (td, J = 8.5, 2.8 Hz, 1H), 1675, 5.32 (qd, J = 6.4, 3.9 Hz, 1H), 4.72 (p, J = 7.3 Hz, 1498, 1H), 3.91 (s, 3H), 2.78 (dd, J = 10.4, 1175, 907, 4.2 Hz, 1H), 2.39 (s, 3H), 2.29 (s, 730 cm.sup.-1 3H), 2.25-2.10 (m, 1H), 1.89 (ddt, J = 14.4, 10.9, 5.2 Hz, 1H), 1.74-1.30 (m, 7H), 1.30-1.13 (m, 2H), 1.06 (d, J = 6.3 Hz, 3H), 1.00-0.78 (m, 1H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 172.09, 168.86, 162.37, 160.90 (d, J = 243.9 Hz), 159.56, 146.64, 141.54, 138.75 (d, J = 7.2 Hz), 137.63, 135.25 (d, J = 3.2 Hz), 129.77 (d, J = 8.1 Hz), 116.34 (d, J = 20.2 Hz), 112.67 (d, J = 20.5 Hz), 109.82, 73.60, 56.31, 49.43, 48.20, 42.91, 31.62, 31.42, 25.12, 24.42, 20.73, 20.61, 18.63, 18.13. .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.78. 181 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.54 (d, film) 3383, calcd for C.sub.28H.sub.36FN.sub.2O.sub.6, J = 7.5 Hz, 1H), 8.35 (d, J = 5.4 Hz, 2928, 515.2552; found, 515.2557 1H), 7.31-7.27 (m, 1H), 7.02 (d, J = 5.4 Hz, 1771, 1H), 6.87-6.73 (m, 2H), 1675, 5.42 (qd, J = 6.3, 4.3 Hz, 1H), 1498, 4.77-4.66 (m, 1H), 3.91 (s, 3H), 2.74 (dd, J = 9.5, 1174, 4.7 Hz, 1H), 2.40 (s, 3H), 1038, 825, 2.31-2.21 (m, 3H), 1.86 (d, J = 12.9 Hz, 1H), 732 cm.sup.-1 1.78-1.49 (m, 3H), 1.41 (d, J = 7.2 Hz, 3H), 1.36-1.15 (m, 3H), 1.15-0.84 (m, 6H), 0.84-0.70 (m, 1H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 172.20, 168.87, 162.36, 160.91 (d, J = 243.8 Hz), 159.55, 146.65, 141.55, 139.40 (d, J = 7.1 Hz), 137.60, 134.70 (d, J = 3.4 Hz), 129.50 (d, J = 7.7 Hz), 116.32 (d, J = 20.6 Hz), 112.74 (d, J = 20.2 Hz), 109.82, 71.63, 56.31, 49.64, 48.13, 40.27, 31.28, 30.87, 29.30, 26.47, 26.37, 26.27, 20.74, 18.66, 18.19. .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.74. 182 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. film) 3384, calcd for C.sub.26H.sub.33FN.sub.2NaO.sub.6, 8.59-8.45 (m, 1H), 8.35 (dd, J = 5.4, 1.3 Hz, 2965, 511.2215; found, 511.2207 1H), 7.31-7.23 (m, 1H), 1771, 7.04-6.95 (m, 1H), 6.83 (dd, J = 9.9, 2.7 Hz, 1H), 1732, 6.76 (dtd, J = 8.5, 5.3, 2.6 Hz, 1H), 1674, 5.42 (ddt, J = 8.6, 6.1, 3.5 Hz, 1H), 1498, 4.76-4.64 (m, 1H), 3.91 (s, 3H), 2.77 (ddd, J = 42.7, 1175, 908, 9.3, 4.8 Hz, 1H), 2.39 (d, J = 2.0 Hz, 731 cm.sup.-1 3H), 2.33-2.23 (m, 3H), 1.97-1.50 (m, 2H), 1.48-1.31 (m, 3H), 1.26 (s, 1H), 1.23-0.93 (m, 4H), 0.94-0.58 (m, 5H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.69, -117.74. 183 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. film) 3380, calcd for C.sub.26H.sub.31FN.sub.2NaO.sub.6, 8.49-8.39 (m, 1H), 8.33 (d, J = 5.4 Hz, 1H), 2938, 509.2058; found, 509.2056 7.09 (dd, J = 8.6, 6.0 Hz, 1H), 7.00 (d, J = 5.5 Hz, 1771, 1H), 6.81 (dd, J = 9.9, 2.9 Hz, 1732, 1H), 6.74 (td, J = 8.4, 2.8 Hz, 1H), 1674, 5.14 (p, J = 6.4 Hz, 1H), 4.59 (p, J = 7.4 Hz, 1498, 1H), 3.90 (s, 3H), 3.02 (dd, J = 10.4, 1175, 908, 6.4 Hz, 1H), 2.70-2.59 (m, 1H), 730 cm.sup.-1 2.39 (s, 3H), 2.34 (s, 3H), 2.17 (d, J = 6.0 Hz, 1H), 1.88-1.59 (m, 4H), 1.42-1.33 (m, 1H), 1.20 (d, J = 7.2 Hz, 3H), 1.17 (d, J = 6.3 Hz, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.62. 184 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.47 (d,

film) 3379, calcd for C.sub.27H.sub.33FN.sub.2NaO.sub.6, J = 8.1 Hz, 1H), 8.31 (d, J = 5.4 Hz, 2949, 523.2215; found, 523.2202 1H), 7.09 (dd, J = 8.7, 5.9 Hz, 1H), 1770, 7.01 (d, J = 5.5 Hz, 1H), 6.84 (td, J = 8.3, 1731, 3.1 Hz, 1H), 6.76 (dd, J = 9.9, 2.8 Hz, 1675, 1H), 5.29 (p, J = 6.7 Hz, 1H), 1499, 4.74-4.63 (m, 1H), 3.91 (s, 3H), 3.10 (dd, J = 9.2, 1175, 907, 7.1 Hz, 1H), 2.40 (d, J = 2.6 Hz, 730 cm.sup.-1 3H), 2.21-2.07 (m, 1H), 1.86 (dtd, J = 14.8, 7.9, 7.1, 4.5 Hz, 1H), 1.67-1.30 (m, 9H), 1.30-1.16 (m, 2H), 1.16-1.08 (m, 4H), 0.98-0.81 (m, 1H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.62. 185 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.52 (d, film) 3379, calcd for C.sub.28H.sub.36FN.sub.2O.sub.6, J = 8.0 Hz, 1H), 8.33 (d, J = 5.4 Hz, 2928, 515.2552; found, 515.2568 1H), 7.05 (dd, J = 8.6, 5.9 Hz, 1H), 1771, 7.01 (d, J = 5.5 Hz, 1H), 6.88-6.78 (m, 1733, 2H), 5.41-5.36 (m, 1H), 1676, 4.77-4.67 (m, 1H), 3.91 (s, 3H), 3.11 (dd, J = 9.0, 1499, 6.1 Hz, 1H), 2.40 (s, 3H), 2.28 (s, 3H), 1193, 1.83-1.39 (m, 10H), 1.31-0.95 (m, 1175, 825, 5H), 0.95-0.81 (m, 2H). 732 cm.sup.-1 .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.48. 186 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.51 (d, film) 3381, calcd for C.sub.25H.sub.31FN.sub.2NaO.sub.6, J = 8.0 Hz, 1H), 8.33 (d, J = 5.4 Hz, 2961, 497.2058; found, 497.2048 1H), 7.05 (dd, J = 8.5, 6.0 Hz, 1H), 1771, 7.01 (d, J = 5.5 Hz, 1H), 6.84 (qd, J = 10.0, 1732, 9.2, 2.8 Hz, 2H), 5.36 (dq, J = 9.3, 6.2 Hz, 1675, 1H), 4.75-4.65 (m, 1H), 3.91 (d, J = 1.9 Hz, 1499, 3H), 3.08 (dd, J = 8.9, 6.5 Hz, 1174, 1H), 2.40 (d, J = 2.1 Hz, 3H), 2.29 (s, 1045, 908, 3H), 2.12 (h, J = 6.8 Hz, 1H), 1.50 (dd, 731 cm.sup.-1 J = 7.2, 2.0 Hz, 3H), 1.06 (d, J = 6.2 Hz, 3H), 0.86 (dd, J = 6.9, 1.9 Hz, 3H), 0.77 (d, J = 6.8 Hz, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 172.23, 168.88, 162.36, 160.94 (d, J = 244.3 Hz), 159.51, 146.65, 141.57, 139.90 (d, J = 6.5 Hz), 137.56, 133.65 (d, J = 2.9 Hz), 129.31-129.08 (m), 116.96 (d, J = 20.5 Hz), 112.33 (d, J = 20.7 Hz), 109.77, 73.76, 56.30, 48.22, 29.69, 29.30, 20.93, 20.91, 20.75, 18.92, 18.59, 17.91. .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.42. 187 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.47 (d, film) 3379, calcd for C.sub.27H.sub.36FN.sub.2O.sub.6, J = 8.3 Hz, 1H), 8.31 (d, J = 5.5 Hz, 2963, 503.2552; found, 503.2557 1H), 7.09 (dd, J = 8.7, 5.9 Hz, 1H), 1771, 7.01 (dd, J = 5.4, 2.2 Hz, 1H), 6.83 (td, J = 8.5, 1732, 3.3 Hz, 1H), 6.76 (dd, J = 9.9, 2.9 Hz, 1675, 1H), 5.41 (dq, J = 7.8, 6.2 Hz, 1H), 1499, 4.70 (dt, J = 8.0, 6.0 Hz, 1H), 3.91 (d, J = 1.7 Hz, 1175, 907, 3H), 3.25 (q, J = 8.0 Hz, 1H), 730 cm.sup.-1 2.40 (s, 3H), 2.27 (s, 2H), 1.62 (d, J = 10.7 Hz, 2H), 1.54-1.24 (m, 6H), 1.09 (d, J = 6.2 Hz, 3H), 1.07-0.81 (m, 4H), 0.81-0.64 (m, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.52. 188 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. film) 3379, calcd for C.sub.26H.sub.33FN.sub.2NaO.sub.6, 8.56-8.45 (m, 1H), 8.32 (dd, J = 5.4, 3.2 Hz, 2964, 511.2215; found, 511.2209 1H), 7.06 (ddd, J = 9.1, 5.8, 3.2 Hz, 1771, 1H), 7.01 (d, J = 5.5 Hz, 1H), 6.83 (qd, 1733, J = 10.4, 9.3, 5.1 Hz, 2H), 5.38 (ddt, J = 18.2, 1676, 9.3, 6.3 Hz, 1H), 4.76-4.63 (m, 1500, 1H), 3.91 (s, 3H), 3.22-3.07 (m, 1H), 1176, 2.40 (d, J = 1.3 Hz, 3H), 1059, 732 cm.sup.-1 2.35-2.25 (m, 3H), 1.95-1.75 (m, 1H), 1.54-1.33 (m, 4H), 1.06 (dd, J = 8.1, 6.2 Hz, 3H), 1.00-0.81 (m, 4H), 0.78 (dt, J = 7.1, 3.7 Hz, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.43, -117.48. 189 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.49 (d, film) 3379, calcd for C.sub.26H.sub.31FN.sub.2NaO.sub.6, J = 8.1 Hz, 1H), 8.33 (d, J = 5.5 Hz, 2939, 509.2059; found, 509.2039 1H), 7.05-6.97 (m, 2H), 1770, 6.87-6.77 (m, 2H), 5.17-5.04 (m, 1H), 1732, 4.74-4.62 (m, 1H), 3.91 (s, 3H), 3.13 (t, J = 8.7 Hz, 1674, 1H), 2.72 (dt, J = 19.2, 9.6 Hz, 1499, 1H), 2.40 (s, 3H), 2.33 (s, 3H), 1175, 908, 2.19-2.06 (m, 1H), 1.92-1.71 (m, 2H), 730 cm.sup.-1 1.71-1.56 (m, 2H), 1.48 (d, J = 7.1 Hz, 3H), 1.44-1.20 (m, 1H), 1.07 (d, J = 6.3 Hz, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.38. 190 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. film) 3383, calcd for C.sub.27H.sub.33FN.sub.2NaO.sub.6, 8.61-8.49 (m, 1H), 8.35 (d, J = 5.4 Hz, 1H), 2951, 523.2215; found, 523.2201 7.33 (dd, J = 8.7, 6.1 Hz, 1H), 7.02 (d, J = 5.5 Hz, 1771, 1H), 6.86-6.72 (m, 2H), 1732, 5.32 (qd, J = 6.4, 3.5 Hz, 1H), 4.74 (p, J = 7.2 Hz, 1675, 1H), 3.92 (s, 3H), 2.77 (dd, J = 10.6, 1498, 3.5 Hz, 1H), 2.40 (s, 3H), 1175, 908, 2.29 (s, 3H), 2.27-2.15 (m, 1H), 730 cm.sup.-1 1.99-1.86 (m, 1H), 1.74-1.29 (m, 7H), 1.29-1.15 (m, 2H), 1.03 (d, J = 6.4 Hz, 3H), 0.93-0.78 (m, 1H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 172.03, 168.89, 162.41, 160.91 (d, J = 243.8 Hz), 159.55, 146.65, 141.52, 138.75 (d, J = 7.2 Hz), 137.62, 135.15 (d, J = 3.2 Hz), 129.97 (d, J = 8.1 Hz), 116.32 (d, J = 20.6 Hz), 112.63 (d, J = 20.5 Hz), 109.81, 73.36, 56.31, 49.51, 48.10, 42.71, 31.73, 31.70, 25.18, 24.52, 20.74, 20.62, 18.55, 17.78. .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.80. 191 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.53 (s, film) 3380, calcd for C.sub.28H.sub.35FN.sub.2NaO.sub.6, 1H), 8.35 (d, J = 5.4 Hz, 1H), 7.33 (dd, 2928, 537.2371; found, 537.2380 J = 8.7, 6.1 Hz, 1H), 7.03 (d, J = 5.4 Hz, 1771, 1H), 6.88-6.69 (m, 2H), 5.42 (pd, 1732, J = 8.5, 7.4, 3.3 Hz, 1H), 1675, 4.78-4.67 (m, 1H), 3.92 (s, 3H), 2.71 (dd, J = 9.9, 1498, 3.9 Hz, 1H), 2.40 (s, 3H), 2.26 (s, 3H), 1173, 909, 1.92 (d, J = 12.8 Hz, 1H), 730 cm.sup.-1 1.79-1.49 (m, 4H), 1.44 (d, J = 7.2 Hz, 3H), 1.38-1.16 (m, 3H), 1.16-0.84 (m, 5H), 0.82-0.66 (m, 1H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 172.01, 168.88, 162.37, 160.90 (d, J = 243.9 Hz), 159.57, 146.64, 141.51, 139.38 (d, J = 7.3 Hz), 137.64, 134.61 (d, J = 3.1 Hz), 129.69 (d, J = 7.8 Hz), 116.28 (d, J = 20.6 Hz), 112.68 (d, J = 20.6 Hz), 109.82, 71.31, 56.32, 49.62, 48.11, 39.95, 31.32, 31.20, 29.29, 26.51, 26.37, 26.24, 20.74, 18.52, 17.93. .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.81. 192 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. film) 3380, calcd for C.sub.25H.sub.31FN.sub.2NaO.sub.6, 8.57-8.43 (m, 1H), 8.35 (d, J = 5.4 Hz, 1H), 2963, 497.2058; found, 497.2059 7.32 (dd, J = 8.7, 6.1 Hz, 1H), 7.02 (d, J = 5.4 Hz, 1771, 1H), 6.83 (dd, J = 9.9, 2.9 Hz, 1732, 1H), 6.79-6.71 (m, 1H), 5.43 (qd, J = 6.4, 1676, 3.9 Hz, 1H), 4.76-4.68 (m, 1H), 1499, 3.92 (s, 3H), 2.67-2.60 (m, 1H), 1176, 733 cm.sup.-1 2.40 (s, 3H), 2.27 (s, 3H), 2.12-1.94 (m, 1H), 1.44 (d, J = 7.2 Hz, 3H), 1.01 (dd, J = 6.4, 3.0 Hz, 6H), 0.67 (d, J = 6.7 Hz, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.77. 193 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.37 (d, film) 3378, calcd for C.sub.28H.sub.35FN.sub.2NaO.sub.7, J = 7.9 Hz, 1H), 8.30 (d, J = 5.4 Hz, 2951, 553.2321; found, 553.2310 1H), 7.31-7.27 (m, 1H), 6.97 (d, J = 5.4 Hz, 1732, 1H), 6.83 (dd, J = 9.9, 2.8 Hz, 1674, 1H), 6.75 (td, J = 8.5, 2.9 Hz, 1H), 1497, 5.75 (d, J = 2.4 Hz, 2H), 5.33 (qd, J = 6.3, 1201, 4.0 Hz, 1H), 4.74 (p, J = 7.3 Hz, 1H), 1003, 968, 3.92 (s, 3H), 2.80 (dd, J = 10.3, 4.2 Hz, 730 cm.sup.-1 1H), 2.29 (s, 3H), 2.25-2.11 (m, 1H), 2.07 (s, 3H), 1.89 (dtd, J = 10.9, 7.1, 3.4 Hz, 1H), 1.77-1.29 (m, 7H), 1.29-1.13 (m, 2H), 1.08 (d, J = 6.3 Hz, 3H), 0.96-0.79 (m, 1H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 172.21, 170.25, 162.95, 160.90 (d, J = 243.9 Hz), 160.39, 145.69, 144.14, 142.51, 138.78 (d, J = 7.2 Hz), 135.27 (d, J = 3.2 Hz), 129.70 (d, J = 8.1 Hz), 116.37 (d, J = 20.5 Hz), 112.69 (d, J = 20.6 Hz), 109.63, 89.63, 73.62, 56.21, 49.42, 48.41, 42.95, 31.62, 31.38, 25.11, 24.41, 20.86, 20.62, 18.50, 18.17. .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.76. 194 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.37 (d, film) 3379, calcd for C.sub.29H.sub.38FN.sub.2O.sub.7, J = 7.8 Hz, 1H), 8.29 (d, J = 5.4 Hz, 2929, 545.2658; found, 545.2652 1H), 7.30 (dd, J = 8.7, 6.1 Hz, 1H), 1733, 6.96 (d, J = 5.4 Hz, 1H), 6.87-6.76 (m, 1675, 2H), 5.75 (d, J = 1.6 Hz, 2H), 1498, 5.48-5.38 (m, 1H), 4.73 (p, J = 7.3 Hz, 1H), 1202, 3.91 (s, 3H), 2.76 (dd, J = 9.3, 4.8 Hz, 1004, 969, 1H), 2.27 (s, 3H), 2.07 (s, 3H), 1.86 (d, 829, 731 cm.sup.-1 J = 12.8 Hz, 1H), 1.81-1.51 (m, 3H), 1.42 (d, J = 7.1 Hz, 3H), 1.33 (d, J = 12.7 Hz, 1H), 1.28-0.89 (m, 8H), 0.85-0.72 (m, 1H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 172.32, 170.25, 162.94, 160.91 (d, J = 244.0 Hz), 160.37, 145.69, 144.10, 142.54, 139.42 (d, J = 7.3 Hz), 134.70 (d, J = 3.3 Hz), 129.47 (d, J = 8.1 Hz), 116.34 (d, J = 20.3 Hz), 112.75 (d, J = 20.5 Hz), 109.62, 89.62, 71.67, 56.21, 49.66, 48.34, 40.30, 31.30, 30.79, 26.45, 26.40, 26.32, 20.86, 20.74, 18.54, 18.23. .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.73. 195 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.31 (d, film) 3379, calcd for C.sub.28H.sub.35FN.sub.2NaO.sub.7, J = 8.1 Hz, 1H), 8.26 (d, J = 5.4 Hz, 2950, 553.2321; found, 553.2326 1H), 7.09 (dd, J = 8.6, 5.9 Hz, 1H), 1756, 6.96 (d, J = 5.4 Hz, 1H), 6.89-6.72 (m, 1676, 2H), 5.74 (s, 2H), 5.36-5.22 (m, 1H), 1498, 4.71 (p, J = 7.2 Hz, 1H), 3.92 (s, 3H), 1201, 3.11 (dd, J = 9.2, 7.2 Hz, 1H), 2.27 (s, 1003, 969, 2H), 2.20-2.10 (m, 2H), 2.07 (s, 4H), 829, 731 cm.sup.-1 1.87 (dtd, J = 14.8, 7.1, 3.4 Hz, 1H), 1.75-1.30 (m, 7H), 1.30-1.16 (m, 1H), 1.11 (d, J = 6.4 Hz, 3H), 0.99-0.81 (m, 1H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.60. 196 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.34 (t, J = 8.5 Hz, film) 3379, calcd for C.sub.27H.sub.35FN.sub.2NaO.sub.7, 1H), 8.28 (dd, J = 5.4, 2.6 Hz, 2964, 541.2321; found, 541.2306 1H), 7.07 (ddd, J = 9.0, 6.0, 3.1 Hz, 1734, 1H), 6.96 (d, J = 5.4 Hz, 1H), 1675, 6.90-6.75 (m, 2H), 5.75 (d, J = 2.7 Hz, 2H), 1498, 5.39 (ddq, J = 18.7, 9.3, 6.2 Hz, 1H), 1202, 4.72 (td, J = 7.4, 6.2 Hz, 1H), 3.92 (s, 1003, 968, 3H), 3.16 (ddd, J = 24.9, 9.0, 6.3 Hz, 829, 731 cm.sup.-1 1H), 2.35-2.20 (m, 3H), 2.07 (d, J = 0.9 Hz, 3H), 1.97-1.72 (m, 1H), 1.58-1.34 (m, 4H), 1.07 (dd, J = 7.7, 6.2 Hz, 3H), 1.02-0.82 (m, 4H), 0.78 (dd, J = 7.3, 5.2 Hz, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.41, -117.46. 197 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.33 (d, film) 3379, calcd for C.sub.27H.sub.34FN.sub.2O.sub.7, J = 7.9 Hz, 1H), 8.28 (d, J = 5.4 Hz, 2977, 517.2345; found, 517.2340 1H), 7.06-6.98 (m, 1H), 6.95 (d, J = 5.4 Hz, 1733, 1H), 6.83 (dd, J = 9.5, 2.3 Hz, 1674, 2H), 5.75 (s, 2H), 5.17-5.01 (m, 1H), 1498, 4.71 (p, J = 7.2 Hz, 1H), 3.91 (s, 3H), 1201, 3.14 (t, J = 8.7 Hz, 1H), 2.73 (p, J = 8.8 Hz, 1041, 1H), 2.34 (s, 3H), 2.23-2.09 (m,

1003, 968, 1H), 2.07 (s, 3H), 1.95-1.72 (m, 2H), 829, 730 cm.sup.-1 1.72-1.55 (m, 2H), 1.50 (d, J = 7.1 Hz, 3H), 1.37 (p, J = 10.0 Hz, 1H), 1.08 (d, J = 6.3 Hz, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.38. 198 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.37 (d, film) 3384, calcd for C.sub.28H.sub.35FN.sub.2NaO.sub.7, J = 7.7 Hz, 1H), 8.30 (d, J = 5.3 Hz, 2951, 553.2321; found, 553.2313 1H), 7.34 (dd, J = 8.7, 6.1 Hz, 1H), 1734, 6.97 (d, J = 5.4 Hz, 1H), 6.83 (dd, J = 9.9, 1677, 2.8 Hz, 1H), 6.74 (td, J = 8.5, 3.0 Hz, 1499, 1H), 5.77 (d, J = 6.4 Hz, 1H), 5.71 (d, J = 6.4 Hz, 1202, 1H), 5.32 (qd, J = 6.4, 3.2 Hz, 1005, 970, 1H), 4.76 (p, J = 7.3 Hz, 1H), 3.92 (s, 830 cm.sup.-1 3H), 2.77 (dd, J = 10.7, 3.5 Hz, 1H), 2.34-2.20 (m, 4H), 2.08 (s, 3H), 1.99-1.86 (m, 1H), 1.74-1.30 (m, 8H), 1.30-1.16 (m, 1H), 1.10-0.99 (m, 3H), 0.84 (ddt, J = 12.2, 10.3, 5.9 Hz, 1H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 172.14, 170.25, 162.99, 160.92 (d, J = 243.9 Hz), 160.41, 145.70, 144.13, 142.50, 138.76 (d, J = 7.3 Hz), 135.17 (d, J = 3.4 Hz), 129.97 (d, J = 8.1 Hz), 116.32 (d, J = 20.7 Hz), 112.61 (d, J = 20.6 Hz), 109.63, 89.62, 73.34, 56.22, 49.52, 48.31, 42.72, 31.73, 31.70, 25.20, 24.53, 20.86, 20.61, 18.46, 17.80. .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.78. 199 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.36 (d, film) 3379, calcd for C.sub.29H.sub.37FN.sub.2NaO.sub.7, J = 7.6 Hz, 1H), 8.30 (d, J = 5.4 Hz, 2928, 567.2477; found, 567.2486 1H), 7.33 (dd, J = 8.7, 6.1 Hz, 1H), 1733, 6.98 (d, J = 5.5 Hz, 1H), 6.82 (dd, J = 9.9, 1675, 2.8 Hz, 1H), 6.71 (td, J = 8.5, 2.9 Hz, 1497, 1H), 5.77 (d, J = 6.4 Hz, 1H), 5.70 (d, J = 6.4 Hz, 1201, 1H), 5.43 (qd, J = 6.2, 3.8 Hz, 1003, 969, 1H), 4.74 (p, J = 7.2 Hz, 1H), 3.92 (s, 911, 829, 3H), 2.72 (dd, J = 9.9, 4.0 Hz, 1H), 730 cm.sup.-1 2.26 (s, 3H), 2.07 (s, 3H), 1.99-1.87 (m, 1H), 1.82-1.51 (m, 3H), 1.51-1.39 (m, 3H), 1.37-1.01 (m, 6H), 0.99 (d, J = 6.3 Hz, 3H), 0.84-0.67 (m, 1H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 172.12, 170.24, 162.93, 160.90 (d, J = 243.7 Hz), 160.44, 145.68, 144.17, 142.45, 139.38 (d, J = 7.2 Hz), 134.63 (d, J = 2.9 Hz), 129.67 (d, J = 8.0 Hz), 116.28 (d, J = 20.5 Hz), 112.64 (d, J = 20.5 Hz), 109.64, 89.64, 71.28, 56.22, 49.62, 48.34, 39.99, 31.31, 31.21, 26.51, 26.37, 26.27, 20.86, 20.73, 18.45, 17.94. .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.79. 200 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 8.56 (s, film) 3383, calcd for C.sub.26H.sub.35N.sub.2O.sub.6, 1H), 8.35 (d, J = 5.4 Hz, 1H), 7.19 (d, J = 7.9 Hz, 2969, 471.2490; found, 471.2485 1H), 7.00 (d, J = 5.4 Hz, 1H), 1772, 6.94 (d, J = 1.9 Hz, 1H), 6.90 (dd, J = 7.9, 1733, 1.9 Hz, 1H), 5.41 (qd, J = 6.3, 4.7 Hz, 1679, 1H), 4.77-4.61 (m, 1H), 3.91 (s, 1200, 1176 cm.sup.-1 3H), 2.68 (dd, J = 9.3, 4.8 Hz, 1H), 2.39 (s, 3H), 2.27 (s, 3H), 2.25 (s, 3H), 2.03 (dp, J = 9.2, 6.6 Hz, 1H), 1.38 (d, J = 7.2 Hz, 3H), 1.05 (d, J = 6.3 Hz, 3H), 0.99 (d, J = 6.6 Hz, 3H), 0.69 (d, J = 6.8 Hz, 3H). 201 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 8.58 (s, film) 3383, calcd for C.sub.28H.sub.37N.sub.2O.sub.6, 1H), 8.35 (d, J = 5.5 Hz, 1H), 7.20 (d, J = 7.9 Hz, 2950, 497.2646; found, 497.2640 1H), 7.01 (d, J = 5.4 Hz, 1H), 1773, 6.97-6.86 (m, 2H), 5.31 (qd, J = 6.3, 1734, 3.9 Hz, 1H), 4.78-4.64 (m, 1H), 1679, 3.91 (s, 3H), 2.79 (dd, J = 10.4, 4.1 Hz, 1H), 1507, 2.40 (s, 3H), 2.27 (s, 3H), 2.26 (s, 3H), 1201, 1177 cm.sup.-1 2.26-2.16 (m, 1H), 1.93-1.82 (m, 1H), 1.71-1.59 (m, 1H), 1.59-1.23 (m, 7H), 1.29-1.15 (m, 1H), 1.07 (d, J = 6.4 Hz, 3H), 0.92-0.83 (m, 1H). 202 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 8.58 (s, film) 3382, calcd for C.sub.29H.sub.38N.sub.2O.sub.6Na, 1H), 8.35 (d, J = 5.4 Hz, 1H), 7.21 (d, J = 7.8 Hz, 2929, 533.2622; found, 533.2615 1H), 7.01 (d, J = 5.5 Hz, 1H),/ 1173, 6.96-6.88 (m, 2H), 5.42 (qd, J = 6.3, 1735, 4.5 Hz, 1H), 4.76-4.67 (m, 1H), 1679, 3.91 (s, 3H), 2.75 (dd, J = 9.4, 4.6 Hz, 1H), 1508, 2.40 (s, 3H), 2.28 (s, 3H), 2.24 (s, 3H), 1201, 1.90-1.50 (m, 5H), 1.41 (d, J = 7.2 Hz, 1176, 735 cm.sup.-1 3H), 1.39-1.31 (m, 1H), 1.29-1.14 (m, 1H), 1.14-1.04 (m, 2H), 1.03 (d, J = 6.3 Hz, 3H), 1.01-0.86 (m, 1H), 0.84-0.73 (m, 1H). 203 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 8.56 (s, film) 2968, calcd for C.sub.27H.sub.37N.sub.2O.sub.6, 1H), 8.35 (dd, J = 5.4, 2.6 Hz, 1H), 29333, 485.2646; found, 485.2643 7.20 (t, J = 7.2 Hz, 1H), 7.06-6.87 (m, 3H), 1773, 5.42 (dtd, J = 10.6, 6.3, 4.5 Hz, 1H), 1734, 4.77-4.62 (m, 1H), 3.91 (s, 3H), 1679, 2.88-2.68 (m, 1H), 2.39 (s, 3H), 1507, 2.29-2.24 (m, 6H), 1.94-1.53 (m, 1H), 1200, 1177 cm.sup.-1 1.46-0.62 (m, 14H). 204 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 8.38 (d, film) 3380, calcd for C.sub.27H.sub.37N.sub.2O.sub.7, J = 7.9 Hz, 1H), 8.29 (d, J = 5.4 Hz, 2969, 501.2595; found, 501.2589 1H), 7.20 (d, J = 7.9 Hz, 1H), 1732, 7.00-6.87 (m, 3H), 5.80-5.69 (m, 2H), 1675, 5.42 (qd, J = 6.2, 4.7 Hz, 1H), 4.71 (p, J = 7.2 Hz, 1502, 1H), 3.91 (s, 3H), 2.69 (dd, J = 9.2, 1200, 4.9 Hz, 1H), 2.27 (s, 3H), 2.25 (s, 1003, 967, 3H), 2.10-1.97 (m, 1H), 2.06 (s, 3H), 829 cm.sup.-1 1.39 (d, J = 7.2 Hz, 3H), 1.07 (d, J = 6.3 Hz, 3H), 0.99 (d, J = 6.6 Hz, 3H), 0.70 (d, J = 6.7 Hz, 3H). 205 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 8.39 (d, film) 3380, calcd for C.sub.29H.sub.39N.sub.2O.sub.7, J = 7.9 Hz, 1H), 8.29 (d, J = 5.4 Hz, 2950, 527.2752; found, 527.2744 1H), 7.21 (d, J = 7.9 Hz, 1H), 1756, 6.98-6.86 (m, 3H), 5.82-5.69 (m, 2H), 1735, 5.32 (qd, J = 6.3, 4.1 Hz, 1H), 4.73 (p, J = 7.3 Hz, 1678, 1H), 3.91 (s, 3H), 2.81 (dd, J = 10.3, 1504, 4.2 Hz, 1H), 2.27 (s, 3H), 2.27 (s, 1202, 1005 cm.sup.-1 3H), 2.25-2.19 (m, 1H), 2.07 (s, 3H), 1.95-1.82 (m, 1H), 1.69-1.60 (m, 1H), 1.57-1.34 (m, 7H), 1.29-1.15 (m, 1H), 1.08 (d, J = 6.3 Hz, 3H), 0.89 (tdd, J = 11.7, 9.4, 7.6 Hz, 1H). 206 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 8.39 (d, film) 3380, calcd for C.sub.30H.sub.40N.sub.2O.sub.7Na, J = 7.9 Hz, 1H), 8.29 (d, J = 5.3 Hz, 2963, 563.2728; found, 563.2725 1H), 7.23 (d, J = 7.7 Hz, 1H), 1756, 6.97-6.90 (m, 3H), 5.81-5.68 (m, 2H), 1735, 5.42 (qd, J = 6.2, 4.6 Hz, 1H), 1678, 4.77-4.69 (m, 1H), 3.91 (s, 3H), 2.76 (dd, J = 9.4, 1504, 4.7 Hz, 1H), 2.28 (s, 3H), 2.24 (s, 3H), 1202, 2.06 (s, 3H), 1.91-1.51z (m, 5H), 1005, 970 cm.sup.-1 1.42 (d, J = 7.2 Hz, 3H), 1.40-1.33 (m, 1H), 1.25-0.91 (m, 7H), 0.85-0.73 (m, 1H). 207 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 8.38 (d, film) 3381, calcd for C.sub.28H.sub.39N.sub.2O.sub.7, J = 16.9, 7.8 Hz, 1H), 8.32-8.26 (m, 2968, 515.2752; found, 515.2746 1H), 7.21 (t, J = 8.3 Hz, 1H), 2933, 7.00-6.86 (m, 3H), 5.81-5.66 (m, 2H), 1757, 5.48-5.37 (m, 1H), 4.77-4.63 (m, 1H), 1735, 3.91 (s, 3H), 2.88-2.70 (m, 1H), 1678, 2.32-2.23 (m, 6H), 2.06 (s, 3H), 1504, 1.90-1.52 (m, 1H), 1.46-0.66 (m, 14H). 1202, 1005 cm.sup.-1 208 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 8.62 (d, film) 2958, calcd for C.sub.25H.sub.31N.sub.2O.sub.6, J = 5.3 Hz, 1H), 7.15 (d, J = 5.4 Hz, 1770, 455.2177; found, 455.2171 1H), 6.90 (d, J = 7.9 Hz, 1H), 1715, 6.87-6.83 (m, 1H), 6.32-6.24 (m, 1H), 1371, 5.65 (q, J = 7.1 Hz, 1H), 5.43 (qd, J = 6.4, 1244, 734 cm.sup.-1 3.2 Hz, 1H), 4.05 (s, 3H), 2.53 (dd, J = 10.4, 3.2 Hz, 1H), 2.18 (s, 3H), 2.10 (s, 3H), 2.06-1.96 (m, 1H), 1.71 (d, J = 7.0 Hz, 3H), 1.04 (d, J = 6.5 Hz, 3H), 0.95 (d, J = 6.3 Hz, 3H), 0.60 (d, J = 6.6 Hz, 3H). 209 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 8.62 (d, film) 2949, calcd for C.sub.27H.sub.33N.sub.2O.sub.6, J = 5.3 Hz, 1H), 7.15 (d, J = 5.4 Hz, 1770, 481.2333; found, 481.2325 1H), 6.93 (d, J = 7.9 Hz, 1H), 1715, 6.87-6.82 (m, 1H), 6.33-6.28 (m, 1H), 1502, 5.67 (q, J = 7.0 Hz, 1H), 5.29 (qd, J = 6.5, 1371, 1243 cm.sup.-1 2.9 Hz, 1H), 4.05 (s, 3H), 2.68 (dd, J = 10.9, 2.8 Hz, 1H), 2.30-2.18 (m, 4H), 2.09 (s, 3H), 1.93 (dtd, J = 11.2, 7.2, 3.4 Hz, 1H), 1.71 (d, J = 7.1 Hz, 3H), 1.68-1.05 (m, 6H), 0.98 (d, J = 6.4 Hz, 3H), 0.83-0.72 (m, 1H). 210 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 8.63 (d, film) 2928, calcd for C.sub.28H.sub.35N.sub.2O.sub.6, J = 5.3 Hz, 1H), 7.15 (d, J = 5.3 Hz, 1771, 495.2490; found, 495.2485 1H), 6.90 (d, J = 7.9 Hz, 1H), 1715, 6.86-6.83 (m, 1H), 6.29-6.24 (m, 1H), 1502, 5.67 (q, J = 7.0 Hz, 1H), 5.43 (qd, J = 6.3, 1371, 1243 cm.sup.-1 3.1 Hz, 1H), 4.06 (s, 3H), 2.66-2.60 (m, 1H), 2.17 (s, 3H), 2.10 (s, 3H), 2.01-1.94 (m, 1H), 1.78-1.54 (m, 6H), 1.53-1.43 (m, 1H), 1.34-1.19 (m, 2H), 1.14-0.88 (m, 6H), 0.76-0.58 (m, 1H). 211 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 14.37 (s, film) 2964, calcd for C.sub.24H.sub.33N.sub.2O.sub.6, 1H), 12.78 (d, J = 7.0 Hz, 1H), 7.88 (d, 1734, 445.2333; found, 445.2370 J = 7.1 Hz, 1H), 7.15 (d, J = 7.7 Hz, 1644, 1H), 6.90 (d, J = 8.0 Hz, 2H), 6.77 (d, J = 7.2 Hz, 1571, 1H), 5.42 (qd, J = 6.3, 5.0 Hz, 1480, 1H), 4.69-4.61 (m, 1H), 3.96 (s, 3H), 1302, 1216 cm.sup.-1 2.69 (dd, J = 9.1, 5.0 Hz, 1H), 2.25 (s, 3H), 2.23 (s, 3H), 2.00 (dp, J = 8.8, 6.6 Hz, 1H), 1.44 (d, J = 7.2 Hz, 3H), 1.08 (d, J = 6.3 Hz, 3H), 0.98 (d, J = 6.6 Hz, 3H), 0.69 (d, J = 6.8 Hz, 3H). 212 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 14.38 (s, film) 2948, calcd for C.sub.26H.sub.35N.sub.2O.sub.6, 1H), 12.79 (d, J = 7.2 Hz, 1H), 7.90 (d, 2868, 471.2490; found, 471.2515 J = 7.1 Hz, 1H), 7.17 (d, J = 7.9 Hz, 1734, 1H), 6.96-6.85 (m, 2H), 6.77 (d, J = 7.1 Hz, 1570, 1H), 5.31 (qd, J = 6.3, 4.0 Hz, 1480, 1H), 4.72-4.60 (m, 1H), 3.96 (s, 3H), 1301, 1218 cm.sup.-1 2.80 (dd, J = 10.3, 4.2 Hz, 1H), 2.28-2.24 (m, 6H), 2.21-2.10 (m, 1H), 1.95-1.85 (m, 1H), 1.69-1.30 (m, 8H), 1.20 (dq, J = 12.3, 9.2 Hz, 1H), 1.08 (d, J = 6.3 Hz, 3H), 0.94-0.81 (m, 1H). 213 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 14.37 (d, film) 2963, calcd for C.sub.25H.sub.35N.sub.2O.sub.6, J = 6.2 Hz, 1H), 12.75 (dd, J = 15.8, 7.1 Hz, 2931, 459.2490; found, 459.2527 1H), 7.98-7.81 (m, 1H), 1733, 7.21-6.71 (m, 4H), 5.50-5.33 (m, 1H), 1569, 4.72-4.58 (m, 1H), 3.96 (s, 3H), 1479, 2.92-2.70 (m, 1H), 2.31-2.19 (m, 6H), 1453, 1.88-1.69 (m, 1H), 1.44 (dd, J = 48.4, 7.2 Hz, 1301, 3H), 1.25-0.58 (m, 11H). 1213, 729 cm.sup.-1 214 IR (thin ESIMS m/z 461.1 .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 8.50 (d, film) 3382, ([M + H].sup.+) J = 8.0 Hz, 1H), 8.33 (d, J = 5.4 Hz, 2962, 1H), 7.17-6.99 (m, 3H), 1770, 6.99-6.86 (m, 2H), 5.38 (dq, J = 8.2, 6.2 Hz, 1H), 1731, 4.75-4.60 (m, 1H), 3.92 (s, 3H), 1674, 2.69 (dd, J = 8.3, 6.9 Hz, 1H), 2.40 (s, 3H), 1590, 2.14-2.00 (m, 1H), 1.49 (d, J = 7.2 Hz, 1571, 3H), 1.08 (d, J = 6.3 Hz, 3H), 1507, 0.87 (d, J = 6.7 Hz, 3H), 0.74 (d, J = 6.7 Hz, 1452, 3H). 1435, .sup.13C NMR (126 MHz, CDCl.sub.3) .delta. 172.15, 1309, 168.93, 162.38, 161.69 (d, J = 244.5 Hz), 1198, 159.48, 146.65, 141.52, 137.54, 1174, 134.34 (d, J = 3.3 Hz), 131.04 (d, J = 7.7 Hz),

1159, 114.75 (d, J = 20.9 Hz), 109.77, 1045, 906, 72.50, 56.31, 55.80, 48.17, 28.29, 833, 803, 21.24, 20.77, 18.75, 18.65, 17.41. 729 cm.sup.-1 215 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.34 (d, film) 3381, calcd for C.sub.26H.sub.34FN.sub.2O.sub.7, J = 7.8 Hz, 1H), 8.28 (d, J = 5.3 Hz, 2962, 505.2345; found, 505.2345 1H), 7.05 (dd, J = 8.5, 5.9 Hz, 1H), 1756, 6.96 (d, J = 5.4 Hz, 1H), 6.91-6.77 (m, 1677, 2H), 5.75 (s, 2H), 5.36 (dq, J = 9.0, 6.2 Hz, 1499, 1H), 4.72 (p, J = 7.2 Hz, 1H), 1203, 3.92 (s, 3H), 3.09 (dd, J = 9.0, 6.4 Hz, 1H), 1044, 2.30 (s, 3H), 2.13 (q, J = 6.8 Hz, 1H), 1004, 971, 2.08 (s, 3H), 1.52 (d, J = 7.2 Hz, 3H), 830 cm.sup.-1 1.07 (d, J = 6.3 Hz, 3H), 0.86 (d, J = 6.7 Hz, 3H), 0.78 (d, J = 6.8 Hz, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 172.35, 170.26, 162.95, 160.94 (d, J = 244.4 Hz), 160.33, 145.69, 144.07, 142.53, 139.88 (d, J = 7.3 Hz), 133.64 (d, J = 3.0 Hz), 129.16 (d, J = 6.0 Hz), 116.96 (d, J = 20.5 Hz), 112.34 (d, J = 20.7 Hz), 109.59, 89.61, 73.75, 56.20, 48.43, 29.70, 29.30, 20.92, 20.87, 18.88, 18.44, 17.99. .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.40. 216 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.45 (d, film) 3382, calcd for C.sub.27H.sub.36FN.sub.2O.sub.6, J = 7.7 Hz, 1H), 8.32 (d, J = 5.4 Hz, 2971, 503.2552; found, 503.2553 1H), 7.05 (dd, J = 8.6, 5.9 Hz, 1H), 1733, 6.99 (d, J = 5.4 Hz, 1H), 6.90-6.73 (m, 1678, 2H), 5.35 (dq, J = 8.9, 6.2 Hz, 1H), 1499, 4.78-4.64 (m, 1H), 3.90 (s, 3H), 3.08 (dd, J = 8.9, 1210, 6.5 Hz, 1H), 2.95 (p, J = 7.0 Hz, 1153, 1H), 2.29 (s, 3H), 2.11 (h, J = 6.7 Hz, 1123, 1H), 1.49 (d, J = 7.2 Hz, 3H), 1.37 (s, 1045, 731 cm.sup.-1 3H), 1.35 (s, 3H), 1.06 (d, J = 6.2 Hz, 3H), 0.86 (d, J = 6.8 Hz, 3H), 0.77 (d, J = 6.8 Hz, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 174.67, 172.31, 162.33, 160.93 (d, J = 244.3 Hz), 159.48, 146.54, 141.94, 139.89 (d, J = 7.3 Hz), 137.73, 133.69 (d, J = 2.9 Hz), 129.15 (d, J = 7.1 Hz), 116.95 (d, J = 20.5 Hz), 112.31 (d, J = 20.7 Hz), 109.62, 73.70, 56.30, 48.19, 33.97, 29.70, 20.93, 20.90, 20.89, 18.95, 18.82, 18.62, 17.90. .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.44. 217 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.60 (d, film) 2960, calcd for C.sub.24H.sub.28FN.sub.2O.sub.6, J = 5.3 Hz, 1H), 7.14 (d, J = 5.3 Hz, 1714, 459.1926; found, 459.1926 1H), 6.97 (dd, J = 8.7, 6.0 Hz, 1H), 1500, 6.62 (td, J = 8.5, 2.9 Hz, 1H), 6.23 (dd, J = 10.0, 1371, 2.8 Hz, 1H), 5.49 (q, J = 7.0 Hz, 1243, 1H), 5.34 (p, J = 6.3 Hz, 1H), 4.07 (s, 1083, 731 cm.sup.-1 3H), 2.87 (dd, J = 9.9, 6.1 Hz, 1H), 2.12 (s, 3H), 1.95 (dp, J = 9.8, 6.6 Hz, 1H), 1.63 (d, J = 7.0 Hz, 3H), 1.15 (d, J = 6.3 Hz, 3H), 1.00 (d, J = 6.5 Hz, 3H), 0.63 (d, J = 6.6 Hz, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.44, -117.49. 218 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 14.33 (s, film) 2962, calcd for C.sub.23H.sub.30FN.sub.2O.sub.6, 1H), 12.78 (d, J = 7.0 Hz, 1H), 7.88 (d, 1736, 449.2082; found, 449.2085 J = 7.2 Hz, 1H), 7.05 (dd, J = 8.3, 5.9 Hz, 1533, 1H), 6.88-6.75 (m, 3H), 5.37 (dq, 1481, J = 8.9, 6.3 Hz, 1H), 4.66 (p, J = 7.1 Hz, 1302, 1H), 3.98 (s, 3H), 3.08 (dd, J = 9.0, 1241, 6.5 Hz, 1H), 2.30 (s, 3H), 2.09 (hept, J = 6.9 Hz, 1155, 1H), 1.57 (d, J = 7.2 Hz, 3H), 1030, 953, 1.07 (d, J = 6.2 Hz, 3H), 0.85 (d, J = 6.8 Hz, 815, 758 cm.sup.-1 3H), 0.77 (d, J = 6.8 Hz, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 171.09, 165.57, 160.90 (d, J = 244.3 Hz), 152.59, 149.34, 139.86 (d, J = 7.3 Hz), 133.66 (d, J = 3.1 Hz), 130.96, 129.20 (d, J = 7.4 Hz), 123.74, 116.84 (d, J = 20.5 Hz), 112.33 (d, J = 20.8 Hz), 107.74, 73.95, 56.55, 48.90, 29.73, 29.30, 20.93, 20.92, 18.96, 17.83, 17.59. .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.36. 219 IR (thin ESIMS m/z 491.2 .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 9.94 (d, film) 3281, ([M + H].sup.+) J = 7.5 Hz, 1H), 8.32 (d, J = 5.4 Hz, 2962, 1H), 7.05 (dd, J = 8.4, 5.9 Hz, 1H), 1770, 7.00 (d, J = 5.5 Hz, 1H), 6.90-6.80 (m, 1733, 2H), 5.39 (dq, J = 9.1, 6.3 Hz, 1H), 1498, 5.18 (p, J = 7.1 Hz, 1H), 3.91 (s, 3H), 1192, 3.10 (dd, J = 9.1, 6.3 Hz, 1H), 2.36 (s, 3H), 1175, 2.30 (s, 3H), 2.19-2.09 (m, 1H), 1104, 821, 1.60 (d, J = 7.1 Hz, 3H), 1.08 (d, J = 6.2 Hz, 730 cm.sup.-1 3H), 0.86 (d, J = 6.7 Hz, 3H), 0.79 (d, J = 6.8 Hz, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 189.28, 171.51, 168.58, 160.96 (d, J = 244.5 Hz), 159.87, 146.29, 145.03, 139.87 (d, J = 7.4 Hz), 136.90, 133.53 (d, J = 2.9 Hz), 129.16 (d, J = 6.9 Hz), 117.00 (d, J = 20.5 Hz), 112.38 (d, J = 20.7 Hz), 109.27, 74.11, 56.43, 53.08, 29.66, 29.29, 21.26, 20.94, 20.91, 18.78, 18.10, 16.84. .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.27. 220 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.49 (d, film) 3382, calcd for C.sub.27H.sub.36FN.sub.2O.sub.7, J = 7.9 Hz, 1H), 8.32 (d, J = 5.4 Hz, 2961, 519.2501; found, 519.2497 1H), 7.05 (dd, J = 8.6, 5.9 Hz, 1H), 1732, 7.01 (d, J = 5.5 Hz, 1H), 6.89-6.77 (m, 1676, 2H), 5.36 (dp, J = 8.9, 6.2 Hz, 1H), 1499, 4.74-4.64 (m, 1H), 3.91 (s, 3H), 3.81 (t, J = 6.6 Hz, 1151, 2H), 3.41 (s, 3H), 3.08 (dd, J = 8.9, 1110, 6.5 Hz, 1H), 2.99 (t, J = 6.6 Hz, 1049, 730 cm.sup.-1 2H), 2.29 (s, 3H), 2.11 (h, J = 6.7 Hz, 1H), 1.49 (d, J = 7.1 Hz, 3H), 1.06 (d, J = 6.3 Hz, 3H), 0.86 (d, J = 6.8 Hz, 3H), 0.77 (d, J = 6.8 Hz, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 172.23, 169.40, 162.30, 160.93 (d, J = 244.3 Hz), 159.51, 146.69, 141.58, 139.89 (d, J = 7.4 Hz), 137.41, 133.65 (d, J = 3.2 Hz), 129.15 (d, J = 9.6 Hz), 116.96 (d, J = 20.5 Hz), 112.32 (d, J = 20.8 Hz), 109.77, 73.74, 67.62, 58.76, 56.33, 48.22, 34.67, 29.70, 20.93, 20.90, 18.95, 18.58, 17.90. .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.42. 221 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.53 (s, film) 3375, calcd for C.sub.25H.sub.32FN.sub.2O.sub.7, 1H), 8.35 (d, J = 5.4 Hz, 1H), 7.21 (dd, 2964, 491.2188; found, 491.2184 J = 8.5, 6.9 Hz, 1H), 7.01 (d, J = 5.4 Hz, 1771, 1H), 6.62-6.48 (m, 2H), 1676, 5.46-5.37 (m, 1H), 4.74-4.64 (m, 1H), 1502, 3.91 (s, 3H), 3.77 (s, 3H), 3.04 (dd, J = 9.5, 1193, 4.8 Hz, 1H), 2.39 (s, 3H), 1.61 (s, 1H), 1035, 953, 1.39 (d, J = 7.2 Hz, 3H), 1.03 (d, J = 6.3 Hz, 832 cm.sup.-1 3H), 0.97 (d, J = 6.6 Hz, 3H), 0.67 (d, J = 6.7 Hz, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -114.24. 222 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.54 (s, film) 3379, calcd for C.sub.27H.sub.36FN.sub.2O.sub.7, 1H), 8.35 (d, J = 5.5 Hz, 1H), 7.23 (dd, 2963, 519.2501; found, 519.2499 J = 8.5, 6.9 Hz, 1H), 7.01 (d, J = 5.5 Hz, 1772, 1H), 6.60-6.49 (m, 2H), 1733, 5.43-5.33 (m, 1H), 4.75-4.65 (m, 1H), 1677, 3.91 (s, 3H), 3.77 (s, 3H), 3.30 (dd, J = 10.0, 1502, 4.4 Hz, 1H), 2.39 (s, 3H), 1194, 1.77-1.59 (m, 2H), 1.51-1.39 (m, 3H), 1.33 (dq, 1177, J = 14.4, 7.2 Hz, 1H), 1.19 (dtd, J = 14.9, 1036, 954, 7.5, 3.3 Hz, 1H), 1.01 (d, J = 6.2 Hz, 834 cm.sup.-1 3H), 0.99-0.91 (m, 1H), 0.88 (t, J = 7.4 Hz, 3H), 0.67 (t, J = 7.4 Hz, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -114.23. 223 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.54 (d, film) 3381, calcd for C.sub.28H.sub.36FN.sub.2O.sub.7, J = 7.8 Hz, 1H), 8.35 (d, J = 5.4 Hz, 2929, 531.2501; found, 531.2496 1H), 7.22 (t, J = 7.7 Hz, 1H), 7.01 (d, J = 5.4 Hz, 1771, 1H), 6.56 (ddd, J = 9.5, 7.3, 1731, 4.1 Hz, 2H), 5.42 (t, J = 5.8 Hz, 1H), 1675, 4.70 (p, J = 7.3 Hz, 1H), 3.91 (s, 3H), 1501, 3.76 (s, 3H), 3.11 (s, 1H), 2.40 (s, 3H), 1193, 1.78 (dd, J = 46.1, 13.0 Hz, 2H), 1175, 953, 1.59 (dd, J = 20.5, 8.6 Hz, 3H), 1.42 (dd, J = 11.2, 731 cm.sup.-1 7.1 Hz, 3H), 1.37-0.85 (m, 8H), 0.83-0.67 (m, 1H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -114.25. 224 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.55 (s, film) 3382, calcd for C.sub.27H.sub.34FN.sub.2O.sub.7, 1H), 8.35 (d, J = 5.4 Hz, 1H), 7.23 (t, J = 7.7 Hz, 2946, 517.2345; found, 517.2341 1H), 7.02 (d, J = 5.4 Hz, 1H), 1771, 6.57 (dd, J = 11.1, 2.6 Hz, 1H), 1731, 6.50 (td, J = 8.4, 2.5 Hz, 1H), 5.32 (dt, J = 10.1, 1675, 5.0 Hz, 1H), 4.72 (p, J = 7.2 Hz, 1501, 1H), 3.92 (s, 3H), 3.77 (s, 3H), 3.11 (d, 1192, J = 10.7 Hz, 1H), 2.40 (s, 3H), 1176, 2.22-2.06 (m, 1H), 1.86 (dtd, J = 11.2, 6.9, 1149, 951, 3.4 Hz, 1H), 1.71-1.59 (m, 2H), 731 cm.sup.-1 1.59-1.29 (m, 5H), 1.29-1.16 (m, 2H), 1.02 (d, J = 6.3 Hz, 3H), 0.88 (dq, J = 11.9, 8.4, 8.0 Hz, 1H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -114.34. 225 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.52 (s, film) 3378, calcd for C.sub.26H.sub.34FN.sub.2O.sub.7, 1H), 8.34 (dd, J = 5.5, 3.2 Hz, 1H), 2964, 505.2345; found, 505.2341 7.21 (ddd, J = 11.8, 8.4, 6.9 Hz, 1H), 1771, 7.01 (dd, J = 5.5, 3.5 Hz, 1H), 6.55 (dddt, J = 13.6, 1731, 8.1, 5.3, 2.7 Hz, 2H), 1675, 5.48-5.36 (m, 1H), 4.75-4.58 (m, 1H), 1501, 3.94-3.87 (m, 3H), 3.77 (d, J = 1.1 Hz, 1193, 3H), 3.16 (ddd, J = 47.2, 9.4, 4.9 Hz, 1175, 1H), 2.39 (d, J = 2.9 Hz, 3H), 1035, 952, 1.86-1.71 (m, 1H), 1.61-1.36 (m, 2H), 833, 732 cm.sup.-1 1.34-1.21 (m, 3H), 1.11-0.93 (m, 4H), 0.89 (td, J = 7.3, 3.6 Hz, 2H), 0.75-0.61 (m, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -114.21, -114.28. 226 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.47 (s, film) 3379, calcd for C.sub.26H.sub.32FN.sub.2O.sub.7, 1H), 8.33 (d, J = 5.4 Hz, 1H), 7.06 (dd, 2938, 503.2188; found, 503.2181 J = 8.5, 6.8 Hz, 1H), 7.01 (d, J = 5.4 Hz, 1771, 1H), 6.55 (dd, J = 11.0, 2.6 Hz, 1731, 1H), 6.48 (td, J = 8.3, 2.5 Hz, 1H), 1675, 5.21 (q, J = 6.1 Hz, 1H), 4.62 (p, J = 7.3 Hz, 1502, 1H), 3.91 (s, 3H), 3.78 (s, 3H), 3.25 (s, 1193, 1H), 2.65 (d, J = 14.9 Hz, 1H), 2.40 (s, 1176, 3H), 2.15-2.06 (m, 1H), 1035, 953, 1.87-1.58 (m, 4H), 1.43 (dt, J = 17.2, 8.4 Hz, 1H), 733 cm.sup.-1 1.30 (d, J = 7.1 Hz, 3H), 1.11 (d, J = 6.3 Hz, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -114.16. 227 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.54 (d, film) 3381, calcd for C.sub.28H.sub.36FN.sub.2O.sub.7, J = 7.8 Hz, 1H), 8.31 (d, J = 5.4 Hz, 2927, 531.2501; found, 531.2493 1H), 7.00 (q, J = 4.9 Hz, 2H), 6.60 (td, 1770, J = 8.3, 2.5 Hz, 1H), 6.53 (dd, J = 11.0, 1732, 2.5 Hz, 1H), 5.54-5.31 (m, 1H), 1675, 4.78-4.63 (m, 1H), 3.91 (s, 3H), 3.73 (s, 3H), 1502, 3.47 (d, J = 69.3 Hz, 1H), 2.40 (s, 3H), 1192, 1.81-1.51 (m, 5H), 1.49 (d, J = 7.1 Hz, 1175, 3H), 1.37-1.08 (m, 2H), 1034, 953, 1.08-1.04 (m, 4H), 1.04-0.70 (m, 3H). 908, 730 cm.sup.-1 .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -114.00. 228 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.50 (s, film) 3379, calcd for C.sub.27H.sub.34FN.sub.2O.sub.7, 1H), 8.28 (d, J = 5.4 Hz, 1H), 7.05 (t, J = 7.7 Hz, 2944, 517.2345; found, 517.2333 1H), 7.00 (d, J = 5.5 Hz, 1H), 1770, 6.58 (td, J = 8.2, 2.5 Hz, 1H), 6.49 (dd, 1732, J = 11.1, 2.5 Hz, 1H), 5.32 (s, 1H), 1675, 4.71-4.59 (m, 1H), 3.91 (s, 3H), 3.71 (s,

1502, 3H), 3.48 (d, J = 40.6 Hz, 1H), 2.40 (s, 1192, 3H), 2.18 (s, 1H), 1.92-1.78 (m, 1H), 1176, 1.63 (s, 1H), 1.56-1.34 (m, 6H), 1149, 1.34-1.20 (m, 2H), 1.11 (d, J = 6.4 Hz, 1033, 952, 3H), 0.89 (td, J = 9.3, 8.3, 3.7 Hz, 1H). 732 cm.sup.-1 .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -114.18. 229 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.53 (s, film) 2963, calcd for C.sub.27H.sub.36FN.sub.2O.sub.7, 1H), 8.30 (d, J = 5.4 Hz, 1H), 1772, 519.2501; found, 519.2499 7.09-6.97 (m, 2H), 6.58 (td, J = 8.2, 2.5 Hz, 1733, 1H), 6.51 (dd, J = 11.0, 2.6 Hz, 1H), 1677, 5.49-5.37 (m, 1H), 4.74-4.63 (m, 1503, 1H), 3.91 (s, 3H), 3.73 (s, 3H), 3.58 (s, 1194, 1H), 2.40 (s, 3H), 1.61 (d, J = 18.5 Hz, 1177, 1H), 1.48 (d, J = 7.1 Hz, 3H), 1035, 954 cm.sup.-1 1.45-1.28 (m, 2H), 1.27-1.12 (m, 1H), 1.09 (d, J = 6.2 Hz, 3H), 1.00-0.83 (m, 4H), 0.74 (t, J = 7.3 Hz, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -113.98. 230 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.55 (s, film) 2964, calcd for C.sub.26H.sub.34FN.sub.2O.sub.7, 1H), 8.31 (dd, J = 8.1, 5.4 Hz, 1H), 1770, 505.2345; found, 505.2333 7.08-6.97 (m, 2H), 6.65-6.55 (m, 1H), 1732, 6.55-6.48 (m, 1H), 5.45 (d, J = 11.2 Hz, 1675, 1H), 4.69 (ddd, J = 14.1, 8.0, 7.1 Hz, 1502, 1H), 3.91 (s, 3H), 3.74 (d, J = 9.6 Hz, 1193, 3H), 3.51 (d, J = 44.9 Hz, 1H), 1175, 2.40 (d, J = 1.8 Hz, 3H), 1.90-1.58 (m, 1034, 953, 1H), 1.55-1.44 (m, 3H), 834, 731 cm.sup.-1 1.41-1.26 (m, 1H), 1.07 (dd, J = 11.1, 6.2 Hz, 3H), 0.99-0.80 (m, 4H), 0.75 (t, J = 7.4 Hz, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -113.91, -114.00. 231 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.51 (d, film) 3381, calcd for C.sub.26H.sub.32FN.sub.2O.sub.7, J = 7.6 Hz, 1H), 8.31 (d, J = 5.4 Hz, 2939, 503.2188; found, 503.2173 1H), 7.02-6.94 (m, 2H), 1770, 6.65-6.49 (m, 2H), 5.16 (s, 1H), 4.73-4.59 (m, 1731, 1H), 3.91 (s, 3H), 3.77 (s, 3H), 3.33 (s, 1674, 1H), 2.78 (hept, J = 8.6, 7.8 Hz, 1H), 1502, 2.40 (s, 3H), 2.17-2.04 (m, 1H), 1193, 1.97-1.56 (m, 4H), 1.45 (d, J = 7.1 Hz, 1175, 3H), 1.43-1.36 (m, 1H), 1.08 (d, J = 6.4 Hz, 1148, 3H). 1035, 953, .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -113.98. 731 cm.sup.-1 232 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.54 (d, film) 3379, calcd for C.sub.25H.sub.32FN.sub.2O.sub.7, J = 7.3 Hz, 1H), 8.31 (d, J = 5.4 Hz, 2962, 491.2188; found, 491.2179 1H), 7.05-6.97 (m, 2H), 6.60 (td, J = 8.3, 1770, 2.6 Hz, 1H), 6.54 (dd, J = 11.1, 2.5 Hz, 1732, 1H), 5.48-5.31 (m, 1H), 1674, 4.77-4.64 (m, 1H), 3.91 (s, 3H), 3.74 (s, 3H), 1502, 3.33 (s, 1H), 2.40 (s, 3H), 1192, 2.14-2.01 (m, 1H), 1.66 (s, 1H), 1.49 (d, J = 7.1 Hz, 1175, 2H), 1.07 (d, J = 6.2 Hz, 3H), 1150, 0.85 (d, J = 6.7 Hz, 3H), 0.72 (d, J = 6.8 Hz, 1034, 953, 3H). 731 cm.sup.-1 .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -113.95. 233 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.36 (d, film) 3381, calcd for C.sub.29H.sub.38FN.sub.2O.sub.8, J = 7.9 Hz, 1H), 8.29 (d, J = 5.4 Hz, 2928, 561.2607; found, 561.2602 1H), 7.26-7.22 (m, 1H), 6.96 (d, J = 5.4 Hz, 1733, 1H), 6.61-6.52 (m, 2H), 1675, 5.78-5.72 (m, 2H), 5.42 (q, J = 5.9 Hz, 1H), 1501, 4.72 (p, J = 7.1 Hz, 1H), 3.91 (s, 3H), 1201, 3.77 (s, 3H), 3.13 (s, 1H), 2.07 (s, 3H), 1004, 953, 1.89-1.51 (m, 7H), 1.42 (d, J = 7.1 Hz, 831, 730 cm.sup.-1 3H), 1.37-1.05 (m, 3H), 1.03 (d, J = 6.2 Hz, 2H), 1.01-0.68 (m, 2H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -114.24. 234 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.37 (d, film) 3381, calcd for C.sub.28H.sub.36FN.sub.2O.sub.8, J = 7.9 Hz, 1H), 8.29 (d, J = 5.4 Hz, 2948, 547.2450; found, 547.2445 1H), 7.28-7.21 (m, 1H), 6.96 (d, J = 5.4 Hz, 1732, 1H), 6.57 (dd, J = 11.1, 2.5 Hz, 1674, 1H), 6.52 (td, J = 8.4, 2.5 Hz, 1H), 1501, 5.81-5.71 (m, 2H), 5.33 (qd, J = 6.4, 3.8 Hz, 1200, 1H), 4.73 (p, J = 7.2 Hz, 1H), 1004, 951, 3.92 (s, 3H), 3.77 (s, 3H), 3.12 (d, J = 10.4 Hz, 831 cm.sup.-1 1H), 2.18 (s, 1H), 2.07 (s, 3H), 1.98-1.80 (m, 1H), 1.64 (d, J = 6.5 Hz, 2H), 1.58-1.29 (m, 5H), 1.29-1.15 (m, 2H), 1.02 (dd, J = 14.6, 6.3 Hz, 3H), 0.94-0.83 (m, 1H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -114.31. 235 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.32 (d, film) 3379, calcd for C.sub.28H.sub.36FN.sub.2O.sub.8, J = 7.8 Hz, 1H), 8.25 (d, J = 5.4 Hz, 2945, 547.2450; found, 547.2444 1H), 7.05 (t, J = 7.7 Hz, 1H), 6.95 (d, J = 5.4 Hz, 1733, 1H), 6.59 (td, J = 8.2, 2.5 Hz, 1674, 1H), 6.50 (dd, J = 11.1, 2.5 Hz, 1H), 1501, 5.74 (s, 2H), 5.32 (s, 1H), 4.68 (p, J = 7.2 Hz, 1200, 1H), 3.91 (s, 3H), 3.73 (s, 3H), 1035, 3.49 (d, J = 46.2 Hz, 1H), 2.07 (s, 3H), 1003, 953, 1.90-1.78 (m, 1H), 1.63 (d, J = 24.2 Hz, 831, 731 cm.sup.-1 1H), 1.55-1.31 (m, 8H), 1.31-1.19 (m, 1H), 1.12 (d, J = 6.4 Hz, 3H), 0.90 (td, J = 9.4, 8.3, 3.6 Hz, 1H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -114.15. 236 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.33 (d, film) 3381, calcd for C.sub.27H.sub.34FN.sub.2O.sub.8, J = 7.9 Hz, 1H), 8.27 (d, J = 5.4 Hz, 2939, 533.2294; found, 533.2286 1H), 7.02-6.92 (m, 2H), 1733, 6.60-6.47 (m, 2H), 5.80-5.70 (m, 2H), 5.16 (s, 1674, 1H), 4.78-4.63 (m, 1H), 3.91 (s, 3H), 1501, 3.78 (s, 3H), 3.34 (s, 1H), 2.79 (h, J = 8.6 Hz, 1200, 1H), 2.20-2.09 (m, 1H), 1147, 2.07 (s, 3H), 1.99-1.57 (m, 4H), 1.48 (dd, J = 7.1, 1037, 3.0 Hz, 3H), 1.45-1.37 (m, 1H), 1003, 953, 1.09 (d, J = 6.4 Hz, 3H). 831, 731 cm.sup.-1 .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -113.97. 237 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.36 (d, film) 3379, calcd for C.sub.26H.sub.34FN.sub.2O.sub.8, J = 7.8 Hz, 1H), 8.27 (d, J = 5.3 Hz, 2962, 521.2294; found, 521.2284 1H), 7.01 (dd, J = 8.5, 6.8 Hz, 1H), 1733, 6.95 (d, J = 5.4 Hz, 1H), 6.60 (td, J = 8.3, 1674, 2.5 Hz, 1H), 6.55 (dd, J = 11.1, 2.5 Hz, 1501, 1H), 5.75 (s, 2H), 5.56-5.31 (m, 1H), 1200, 4.71 (p, J = 7.3 Hz, 1H), 3.92 (s, 3H), 1036, 3.75 (s, 3H), 3.34 (s, 1H), 2.07 (s, 3H), 1003, 953, 1.67 (s, 1H), 1.51 (d, J = 7.1 Hz, 3H), 831, 731 cm.sup.-1 1.08 (d, J = 6.3 Hz, 3H), 0.85 (d, J = 6.8 Hz, 3H), 0.73 (d, J = 6.8 Hz, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -113.93. 238 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.49 (s, film) 3380, calcd for C.sub.28H.sub.36FN.sub.2O.sub.8, 1H), 8.31 (d, J = 5.4 Hz, 1H), 6.98 (dd, 2937, 547.2450; found, 547.2439 J = 15.2, 6.2 Hz, 2H), 6.61-6.46 (m, 1768, 2H), 5.16 (s, 1H), 4.70-4.59 (m, 1H), 1732, 3.90 (s, 3H), 3.82 (t, J = 6.6 Hz, 2H), 1675, 3.77 (s, 3H), 3.41 (s, 3H), 1502, 3.37-3.23 (m, 1H), 2.99 (t, J = 6.7 Hz, 2H), 1146, 2.77 (h, J = 8.8, 8.4 Hz, 1H), 2.16-2.05 (m, 1110, 1H), 1.97-1.55 (m, 5H), 1.44 (d, J = 7.2 Hz, 1035, 953, 3H), 1.08 (d, J = 6.4 Hz, 3H). 833, 731 cm.sup.-1 .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -113.97. 239 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.52 (s, film) 3377, calcd for C.sub.27H.sub.36FN.sub.2O.sub.8, 1H), 8.31 (d, J = 5.4 Hz, 1H), 2961, 535.2450; found, 535.2441 7.07-6.97 (m, 2H), 6.60 (td, J = 8.3, 2.6 Hz, 1768, 1H), 6.54 (dd, J = 11.0, 2.5 Hz, 1H), 1675, 5.49-5.35 (m, 1H), 4.72-4.60 (m, 1502, 1H), 3.90 (s, 3H), 3.81 (t, J = 6.6 Hz, 1310, 2H), 3.74 (s, 3H), 3.41 (s, 3H), 3.28 (d, 1148, J = 41.3 Hz, 1H), 2.99 (t, J = 6.6 Hz, 1112, 2H), 2.08 (dp, J = 13.6, 7.0 Hz, 1H), 1034, 953, 1.48 (d, J = 7.1 Hz, 3H), 1.07 (d, J = 6.2 Hz, 833, 732 cm.sup.-1 3H), 0.85 (d, J = 6.7 Hz, 3H), 0.72 (d, J = 6.9 Hz, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -113.94. 240 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. film) 1733, calcd for C.sub.28H.sub.37N.sub.2O.sub.7, 8.35-8.23 (m, 2H), 7.02 (d, J = 7.9 Hz, 1H), 1674, 513.2595; found, 513.2591 6.95-6.84 (m, 3H), 5.79-5.68 (m, 1503, 2H), 5.20-5.08 (m, 1H), 1201, 4.66-4.55 (m, 1H), 3.90 (s, 3H), 3.04 (dd, J = 10.5, 1003, 968, 6.3 Hz, 1H), 2.70 (dh, J = 16.8, 911, 729 cm.sup.-1 8.8, 8.2 Hz, 1H), 2.32 (s, 3H), 2.24 (s, 3H), 2.19-2.10 (m, 1H), 2.06 (s, 3H), 1.89-1.63 (m, 4H), 1.46-1.36 (m, 1H), 1.21 (d, J = 7.2 Hz, 3H), 1.18 (d, J = 6.3 Hz, 3H). 241 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 8.48 (s, film) 2938, calcd for C.sub.27H.sub.35N.sub.2O.sub.6, 1H), 8.33 (d, J = 5.5 Hz, 1H), 1771, 483.2490; found, 483.2484 7.04-6.85 (m, 4H), 5.20-5.10 (m, 1H), 1675, 4.65-4.52 (m, 1H), 3.90 (s, 3H), 3.03 (dd, J = 10.5, 1505, 6.3 Hz, 1H), 2.69 (h, J = 9.1 Hz, 1199, 1H), 2.39 (s, 3H), 2.32 (s, 3H), 2.25 (s, 1175, 908, 3H), 2.20-2.10 (m, 1H), 730 cm.sup.-1 1.88-1.63 (m, 4H), 1.46-1.35 (m, 1H), 1.20 (d, J = 7.1 Hz, 3H), 1.16 (d, J = 6.4 Hz, 3H). 242 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.49 (d, film) 3380, calcd for J = 8.1 Hz, 1H), 8.34 (d, J = 5.5 Hz, 2961, C.sub.24H.sub.30ClN.sub.2O.sub.6, 479.1769; 1H), 7.21 (d, J = 8.4 Hz, 2H), 1771, found, 479.1772 7.07-6.97 (m, 3H), 5.46-5.33 (m, 1H), 1734, 4.75-4.61 (m, 1H), 3.92 (s, 3H), 2.68 (t, J = 7.6 Hz, 1676, 1H), 2.40 (s, 3H), 1508, 2.12-2.02 (m, 1H), 1.49 (d, J = 7.1 Hz, 3H), 1310, 1.08 (d, J = 6.3 Hz, 3H), 0.88 (d, J = 6.6 Hz, 1200, 3H), 0.73 (d, J = 6.8 Hz, 3H). 1175, 1061, 827 cm.sup.-1 243 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.54 (s, film) 3380, calcd for C.sub.25H.sub.32FN.sub.2O.sub.6, 1H), 8.34 (d, J = 5.4 Hz, 1H), 2962, 476.2271; found, 476.2275 7.11-6.97 (m, 2H), 6.83-6.64 (m, 2H), 1772, 5.44-5.29 (m, 1H), 4.77-4.60 (m, 1H), 1735, 3.92 (s, 3H), 2.71-2.60 (m, 1H), 1677, 2.40 (s, 3H), 2.24 (d, J = 1.8 Hz, 3H), 1508, 2.13-2.00 (m, 1H), 1.49 (d, J = 7.1 Hz, 3H), 1202, 1.09 (d, J = 6.3 Hz, 3H), 0.86 (d, J = 6.8 Hz, 1176, 1061 cm.sup.-1 3H), 0.75 (d, J = 6.7 Hz, 3H). 244 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.48 (d, film) 3382, calcd for C.sub.24H.sub.29F.sub.2N.sub.2O.sub.6, J = 8.1 Hz, 1H), 8.33 (d, J = 5.4 Hz, 2963, 480.202; found, 480.202 1H), 7.08-6.97 (m, 2H), 6.92 (ddd, J = 11.7, 1771, 7.6, 2.2 Hz, 1H), 6.85-6.72 (m, 1734, 1H), 5.41-5.26 (m, 1H), 1676, 4.75-4.63 (m, 1H), 3.92 (s, 3H), 2.73-2.57 (m, 1513, 1H), 2.40 (s, 3H), 2.12-1.99 (m, 1H), 1203, 1.48 (d, J = 7.1 Hz, 3H), 1.09 (d, J = 6.3 Hz, 1175, 1061 cm.sup.-1 3H), 0.89 (d, J = 6.5 Hz, 3H), 0.74 (d, J = 6.7 Hz, 3H). 245 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.53 (d, film) 3380, calcd for C.sub.27H.sub.37N.sub.2O.sub.7, J = 8.0 Hz, 1H), 8.34 (d, J = 5.5 Hz, 2960, 501.2595; found, 501.2589 1H), 7.06 (t, J = 7.0 Hz, 2H), 1769, 7.02-6.95 (m, 3H), 5.39 (dq, J = 8.7, 6.2 Hz, 1732, 1H), 4.74-4.63 (m, 1H), 3.90 (s, 3H), 1676, 3.81 (t, J = 6.6 Hz, 2H), 3.40 (s, 3H), 1508, 2.99 (t, J = 6.6 Hz, 2H), 2.67 (dd, J = 8.7, 1210, 6.3 Hz, 1H), 2.32 (s, 3H), 2.09 (h, J = 6.7 Hz, 1111, 1H), 1.50 (d, J = 7.1 Hz, 3H), 1061, 823 cm.sup.-1 1.08 (d, J = 6.3 Hz, 3H), 0.85 (d, J = 6.8 Hz, 3H), 0.75 (d, J = 6.8 Hz, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 172.29, 169.42, 162.35, 159.50, 146.71, 141.69, 137.40, 136.06, 135.51, 129.68, 128.62, 109.74, 72.83, 67.62, 58.76, 56.32, 56.24, 48.23, 34.66, 28.22, 21.36, 21.01, 18.68, 18.57, 17.84. 246 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz,

CDCl.sub.3) .delta. 8.51 (d, film) 3380, calcd for C.sub.27H.sub.36FN.sub.2O.sub.7, J = 7.7 Hz, 1H), 8.33 (d, J = 5.5 Hz, 2961, 519.2501; found, 519.2498 1H), 7.01 (d, J = 5.5 Hz, 1H), 1733, 6.93-6.80 (m, 3H), 5.36 (dq, J = 8.6, 6.3 Hz, 1676, 1H), 4.73-4.62 (m, 1H), 3.91 (s, 3H), 1503, 3.81 (t, J = 6.6 Hz, 2H), 3.40 (s, 3H), 1208, 2.99 (t, J = 6.6 Hz, 2H), 2.65 (dd, J = 8.6, 1115, 6.6 Hz, 1H), 2.24 (d, J = 1.9 Hz, 1051, 731 cm.sup.-1 3H), 2.08 (hept, J = 6.7 Hz, 1H), 1.49 (d, J = 7.2 Hz, 3H), 1.08 (d, J = 6.3 Hz, 3H), 0.85 (d, J = 6.7 Hz, 3H), 0.74 (d, J = 6.8 Hz, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 172.24, 169.42, 162.36, 160.27 (d, J = 243.5 Hz), 159.52, 146.72, 141.64, 137.42, 134.08 (d, J = 3.9 Hz), 132.56 (d, J = 5.0 Hz), 128.37 (d, J = 7.7 Hz), 124.07 (d, J = 17.1 Hz), 114.38 (d, J = 22.0 Hz), 109.78, 72.67, 67.62, 58.76, 56.33, 55.84, 48.22, 34.67, 28.28, 21.30, 18.67, 18.63, 17.67, 14.63 (d, J = 3.6 Hz). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -120.90. 247 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.53 (d, film) 3377, calcd for C.sub.27H.sub.36FN.sub.2O.sub.8, J = 7.7 Hz, 1H), 8.33 (d, J = 5.4 Hz, 2962, 535.2450; found, 535.2446 1H), 7.06-6.97 (m, 2H), 1734, 6.69-6.62 (m, 1H), 6.58 (dd, J = 12.0, 2.6 Hz, 1676, 1H), 5.40 (ddt, J = 8.6, 6.8, 3.4 Hz, 1H), 1507, 4.75-4.60 (m, 1H), 3.90 (s, 3H), 1209, 3.81 (t, J = 6.6 Hz, 2H), 3.78 (s, 3H), 3.40 (s, 1113, 3H), 3.09 (t, J = 7.6 Hz, 1H), 2.99 (t, J = 6.6 Hz, 1061, 833, 2H), 2.10 (h, J = 6.8 Hz, 1H), 731 cm.sup.-1 1.49 (d, J = 7.1 Hz, 3H), 1.10 (d, J = 6.3 Hz, 3H), 0.93-0.87 (m, 3H), 0.75 (d, J = 6.7 Hz, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 172.25, 169.41, 162.33, 162.10 (d, J = 244.3 Hz), 159.48, 159.32 (d, J = 11.2 Hz), 146.71, 141.67, 137.38, 130.69 (d, J = 6.6 Hz), 117.57 (d, J = 15.3 Hz), 109.73, 109.58 (d, J = 2.9 Hz), 101.39 (d, J = 28.0 Hz), 72.48, 67.62, 58.76, 56.31, 55.44, 48.21, 34.66, 29.29, 28.36, 21.10, 18.97, 18.50, 17.43. .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -112.98. 248 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.51 (d, film) 3380, calcd for C.sub.27H.sub.36FN.sub.2O.sub.8, J = 7.9 Hz, 1H), 8.34 (d, J = 5.4 Hz, 2962, 535.2450; found, 535.2444 1H), 7.01 (d, J = 5.5 Hz, 1H), 1732, 6.92-6.75 (m, 3H), 5.34 (dq, J = 8.3, 6.2 Hz, 1676, 1H), 4.66 (dt, J = 8.1, 7.1 Hz, 1H), 1511, 3.90 (s, 3H), 3.86 (s, 3H), 3.81 (t, J = 6.6 Hz, 1273, 2H), 3.40 (s, 3H), 2.99 (t, J = 6.6 Hz, 1210, 2H), 2.64 (dd, J = 8.6, 6.5 Hz, 1H), 1113, 731 cm.sup.-1 2.05 (h, J = 6.8 Hz, 1H), 1.49 (d, J = 7.2 Hz, 3H), 1.09 (d, J = 6.3 Hz, 3H), 0.87 (d, J = 6.7 Hz, 3H), 0.75 (d, J = 6.7 Hz, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 172.19, 169.42, 162.36, 159.51, 151.94 (d, J = 245.0 Hz), 146.73, 146.25 (d, J = 10.8 Hz), 141.62, 137.42, 131.84 (d, J = 5.6 Hz), 125.47 (d, J = 3.6 Hz), 117.15 (d, J = 18.2 Hz), 113.05-112.84 (m), 109.77, 72.51, 67.62, 58.76, 56.33, 56.24, 55.74, 48.21, 34.67, 28.35, 21.25, 18.77, 18.63, 17.47. .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -135.76. 249 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.55 (s, film) 3379, calcd for C.sub.28H.sub.39N.sub.2O.sub.8, 1H), 8.32 (d, J = 5.4 Hz, 1H), 6.99 (d, J = 5.5 Hz, 2960, 531.2701; found, 531.2703 1H), 6.94 (d, J = 7.7 Hz, 1H), 1769, 6.75-6.69 (m, 1H), 6.65 (d, J = 1.6 Hz, 1732, 1H), 5.41 (d, J = 7.8 Hz, 1H), 1678, 4.73-4.62 (m, 1H), 3.90 (s, 3H), 3.82 (t, J = 6.6 Hz, 1506, 2H), 3.75 (s, 3H), 3.40 (s, 3H), 1311, 2.99 (t, J = 6.7 Hz, 2H), 2.31 (s, 3H), 1210, 2.09 (h, J = 6.7 Hz, 1H), 1.69 (s, 1H), 1111, 1.49 (d, J = 7.1 Hz, 3H), 1.07 (d, J = 6.2 Hz, 1041, 808 cm.sup.-1 3H), 0.84 (d, J = 6.7 Hz, 3H), 0.74 (d, J = 6.8 Hz, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 172.30, 169.43, 162.30, 159.47, 158.10, 146.70, 141.75, 137.36, 137.15, 124.61, 120.69, 111.71, 109.69, 73.50, 67.63, 58.76, 56.31, 55.31, 48.32, 34.67, 29.30, 28.80, 21.43, 21.12, 18.87, 18.61, 18.11. 250 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.53 (d, film) 3381, calcd for C.sub.25H.sub.32FN.sub.2O.sub.6, J = 8.0 Hz, 1H), 8.34 (d, J = 5.4 Hz, 2962, 475.2239; found, 475.2236 1H), 7.01 (d, J = 5.5 Hz, 1H), 1771, 6.92-6.84 (m, 3H), 5.36 (dq, J = 8.6, 6.3 Hz, 1733, 1H), 4.69 (dq, J = 8.1, 7.1 Hz, 1H), 1677, 3.91 (s, 3H), 2.70-2.62 (m, 1H), 2.40 (s, 1503, 3H), 2.24 (d, J = 1.9 Hz, 3H), 2.07 (h, J = 6.7 Hz, 1311, 1H), 1.50 (d, J = 7.1 Hz, 3H), 1203, 1.08 (d, J = 6.2 Hz, 3H), 0.85 (d, J = 6.7 Hz, 1176, 3H), 0.74 (d, J = 6.8 Hz, 3H). 1049, 733 cm.sup.-1 .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 172.23, 168.89, 162.41, 160.27 (d, J = 243.4 Hz), 159.51, 146.66, 141.63, 137.57, 134.08 (d, J = 3.8 Hz), 132.56 (d, J = 4.9 Hz), 128.37 (d, J = 7.7 Hz), 124.08 (d, J = 17.2 Hz), 114.38 (d, J = 22.0 Hz), 109.78, 72.69, 56.30, 55.84, 48.22, 28.28, 21.30, 20.75, 18.67, 18.64, 17.67, 14.63 (d, J = 3.6 Hz). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -120.91. 251 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.55 (d, film) 3376, calcd for C.sub.25H.sub.32FN.sub.2O.sub.7, J = 7.7 Hz, 1H), 8.33 (d, J = 5.4 Hz, 2963, 491.2188; found, 491.2183 1H), 7.06-6.97 (m, 2H), 6.65 (ddd, J = 8.6, 1771, 2.6, 0.8 Hz, 1H), 6.58 (dd, J = 12.0, 1733, 2.6 Hz, 1H), 5.41 (dqd, J = 7.6, 6.2, 1.2 Hz, 1675, 1H), 4.68 (dq, J = 8.1, 7.2 Hz, 1H), 1507, 3.91 (s, 3H), 3.78 (s, 3H), 1195, 3.15-3.03 (m, 1H), 2.40 (s, 3H), 2.14-2.05 (m, 1175, 1H), 1.50 (d, J = 7.2 Hz, 3H), 1.10 (d, J = 6.3 Hz, 1150, 3H), 0.90 (dd, J = 6.7, 0.8 Hz, 1033, 833, 3H), 0.75 (d, J = 6.7 Hz, 3H). 731 cm.sup.-1 .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 172.24, 168.89, 162.39, 162.11 (d, J = 244.3 Hz), 159.49, 159.34 (d, J = 11.2 Hz), 146.66, 141.67, 137.54, 130.71 (d, J = 6.5 Hz), 117.58 (d, J = 15.5 Hz), 109.73, 109.59 (d, J = 3.0 Hz), 101.40 (d, J = 27.9 Hz), 72.50, 56.29, 55.45, 48.22, 29.30, 28.37, 21.10, 20.75, 18.98, 18.51, 17.42. .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -112.96. 252 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.53 (d, film) 3379, calcd for C.sub.25H.sub.32FN.sub.2O.sub.7, J = 8.0 Hz, 1H), 8.34 (d, J = 5.4 Hz, 2962, 491.2188; found, 491.2182 1H), 7.01 (d, J = 5.5 Hz, 1H), 1770, 6.90-6.76 (m, 3H), 5.34 (dq, J = 8.4, 6.3 Hz, 1732, 1H), 4.73-4.63 (m, 1H), 3.91 (s, 3H), 1675, 3.86 (s, 3H), 2.68-2.61 (m, 1H), 1512, 2.40 (s, 3H), 2.05 (dq, J = 13.5, 6.8 Hz, 1H), 1202, 1.49 (d, J = 7.2 Hz, 3H), 1.09 (d, J = 6.3 Hz, 1176, 3H), 0.87 (d, J = 6.7 Hz, 3H), 1030, 731 cm.sup.-1 0.75 (d, J = 6.7 Hz, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 172.17, 168.90, 162.41, 159.50, 151.94 (d, J = 245.0 Hz), 146.68, 146.25 (d, J = 10.6 Hz), 141.59, 137.56, 131.84 (d, J = 5.7 Hz), 125.48 (d, J = 3.6 Hz), 117.13 (d, J = 18.2 Hz), 112.94 (d, J = 1.6 Hz), 109.77, 72.53, 56.27 (d, J = 6.4 Hz), 55.73, 48.21, 29.29, 28.35, 21.25, 20.75, 18.76, 18.64, 17.47. .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -135.76. 253 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.57 (d, film) 3381, calcd for C.sub.26H.sub.35N.sub.2O.sub.7, J = 7.9 Hz, 1H), 8.32 (d, J = 5.4 Hz, 2961, 487.2439; found, 487.2430 1H), 7.00 (d, J = 5.5 Hz, 1H), 6.94 (d, J = 7.7 Hz, 1772, 1H), 6.75-6.68 (m, 1H), 1732, 6.65 (d, J = 1.6 Hz, 1H), 1678, 5.51-5.39 (m, 1H), 4.76-4.60 (m, 1H), 3.90 (s, 1507, 3H), 3.75 (s, 3H), 3.33 (s, 1H), 2.40 (s, 1201, 3H), 2.31 (s, 3H), 2.09 (h, J = 6.7 Hz, 1176, 1H), 1.50 (d, J = 7.1 Hz, 3H), 1.07 (d, J = 6.2 Hz, 1041, 733 cm.sup.-1 3H), 0.84 (d, J = 6.8 Hz, 3H), 0.74 (d, J = 6.8 Hz, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 172.29, 168.90, 162.35, 159.46, 158.10, 146.65, 141.73, 137.51, 137.15, 124.61, 120.69, 111.71, 109.69, 73.52, 56.28, 55.31, 48.33, 29.30, 28.80, 21.43, 21.13, 20.75, 18.85, 18.62, 18.11. 254 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.55 (d, film) 3379, calcd for C.sub.26H.sub.35N.sub.2O.sub.7, J = 8.0 Hz, 1H), 8.33 (d, J = 5.4 Hz, 2959, 487.2439; found, 487.2436 1H), 7.06-6.92 (m, 2H), 6.70 (d, J = 8.1 Hz, 1771, 2H), 5.35 (dq, J = 9.2, 6.2 Hz, 1731, 1H), 4.70 (dq, J = 8.1, 7.1 Hz, 1H), 1677, 3.91 (s, 3H), 3.78 (s, 3H), 3.06 (dd, J = 9.3, 1503, 6.0 Hz, 1H), 2.40 (s, 3H), 2.29 (s, 3H), 1201, 2.12 (dq, J = 13.4, 6.7 Hz, 1H), 1.51 (d, 1175, J = 7.1 Hz, 3H), 1.05 (d, J = 6.2 Hz, 1046, 733 cm.sup.-1 3H), 0.84 (d, J = 6.8 Hz, 3H), 0.79 (d, J = 6.9 Hz, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 172.34, 168.88, 162.37, 159.49, 157.56, 146.65, 141.65, 138.91, 137.54, 130.04, 128.84, 115.90, 110.86, 109.74, 74.13, 56.29, 55.05, 48.27, 29.64, 29.30, 21.09, 20.99, 20.75, 18.74, 18.61, 18.26. 255 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.37 (d, film) 3379, calcd for C.sub.26H.sub.35N.sub.2O.sub.7, J = 7.8 Hz, 1H), 8.29 (d, J = 5.3 Hz, 2961, 487.2439; found, 487.2433 1H), 7.11-7.03 (m, 2H), 1756, 7.03-6.93 (m, 3H), 5.75 (d, J = 0.6 Hz, 2H), 1675, 5.40 (dq, J = 8.8, 6.3 Hz, 1H), 1503, 4.79-4.66 (m, 1H), 3.91 (s, 3H), 2.68 (dd, J = 8.8, 1201, 6.3 Hz, 1H), 2.32 (s, 3H), 1042, 2.16-2.03 (m, 4H), 1.53 (d, J = 7.1 Hz, 3H), 1003, 969, 1.09 (d, J = 6.3 Hz, 3H), 0.85 (d, J = 6.8 Hz, 827, 731 cm.sup.-1 3H), 0.76 (d, J = 6.8 Hz, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 172.40, 170.26, 162.98, 160.32, 145.70, 144.04, 142.66, 136.08, 135.50, 129.69, 128.62, 109.55, 89.63, 72.83, 56.26, 56.19, 48.44, 28.23, 21.36, 21.01, 20.87, 18.57, 18.54, 17.89. 256 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.36 (d, film) 3380, calcd for C.sub.26H.sub.34FN.sub.2O.sub.7, J = 7.7 Hz, 1H), 8.29 (d, J = 5.4 Hz, 2962, 505.2345; found, 505.2339 1H), 6.96 (d, J = 5.4 Hz, 1H), 1735, 6.93-6.85 (m, 3H), 5.75 (s, 2H), 5.37 (dq, J = 8.6, 1674, 6.2 Hz, 1H), 4.78-4.65 (m, 1H), 1503, 3.92 (s, 3H), 2.67 (dd, J = 8.6, 6.5 Hz, 1203, 1H), 2.24 (d, J = 2.0 Hz, 3H), 2.07 (s, 1043, 4H), 1.52 (d, J = 7.2 Hz, 3H), 1.09 (d, J = 6.3 Hz, 1004, 969, 3H), 0.85 (d, J = 6.7 Hz, 3H), 829, 731 cm.sup.-1 0.75 (d, J = 6.8 Hz, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 172.35, 170.27, 163.00, 160.33, 160.28 (d, J = 243.4 Hz), 145.71, 144.07, 142.60, 134.07 (d, J = 3.8 Hz), 132.59 (d, J = 4.9 Hz), 128.35 (d, J = 7.7 Hz), 124.09 (d, J = 17.2 Hz), 114.38 (d, J = 22.1 Hz), 109.59, 89.62, 72.67, 56.20, 55.85, 48.43, 28.28, 21.31, 20.87, 18.62, 18.51, 17.74, 14.63 (d, J = 3.5 Hz). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -120.87. 257 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.37 (d, film) 3380, calcd for C.sub.26H.sub.34FN.sub.2O.sub.8, J = 7.8 Hz, 1H), 8.28 (d, J = 5.4 Hz, 2963, 521.2294; found, 521.2286 1H), 7.03 (t, J = 8.5 Hz, 1H), 6.95 (d = 5.4 Hz, 1736, 1H), 6.66 (ddd, J = 8.6, 2.6, 1676, 0.7 Hz, 1H), 6.58 (dd, J = 12.0, 2.6 Hz, 1507, 1H), 5.78-5.68 (m, 2H), 1200, 5.47-5.36 (m, 1H), 4.75-4.65 (m, 1H), 3.91 (s, 1040, 3H), 3.79 (s, 3H), 3.10 (t, J = 7.7 Hz,

1004, 969, 1H), 2.07 (s, 4H), 1.52 (d, J = 7.2 Hz, 831 cm.sup.-1 3H), 1.11 (d, J = 6.3 Hz, 3H), 0.90 (dd, J = 6.7, 0.8 Hz, 3H), 0.76 (d, J = 6.7 Hz, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 172.36, 170.27, 162.99, 162.11 (d, J = 244.3 Hz), 160.32, 159.34 (d, J = 11.2 Hz), 145.70, 144.04, 142.64, 130.70 (d, J = 5.5 Hz), 117.58 (d, J = 15.5 Hz), 109.58 (d, J = 3.3 Hz), 109.55, 101.40 (d, J = 27.9 Hz), 89.63, 72.58-72.37 (m), 56.19, 55.45, 48.42, 29.30, 28.39, 21.10, 20.87, 18.98, 18.37, 17.44. .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -112.98. 258 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.36 (d, film) 3378, calcd for C.sub.26H.sub.34FN.sub.2O.sub.8, J = 7.8 Hz, 1H), 8.29 (d, J = 5.4 Hz, 2962, 521.2294; found, 521.2288 1H), 6.96 (d, J = 5.4 Hz, 1H), 1736, 6.90-6.76 (m, 3H), 5.75 (s, 2H), 5.35 (dq, J = 8.5, 1674, 6.3 Hz, 1H), 4.70 (p, J = 7.2 Hz, 1513, 1H), 3.92 (s, 3H), 3.87 (s, 3H), 1203, 2.69-2.60 (m, 1H), 2.13-2.01 (m, 4H), 1043, 1.52 (d, J = 7.1 Hz, 3H), 1.10 (d, J = 6.3 Hz, 1004, 969, 3H), 0.87 (d, J = 6.7 Hz, 3H), 0.76 (d, J = 6.7 Hz, 732 cm.sup.-1 3H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 172.31, 170.27, 163.01, 160.33, 151.95 (d, J = 245.4 Hz), 146.27 (d, J = 10.8 Hz), 145.72, 144.07, 142.57, 131.82 (d, J = 5.8 Hz), 125.46 (d, J = 3.5 Hz), 117.16 (d, J = 18.0 Hz), 113.05-112.84 (m), 109.59, 89.62, 72.51, 56.22 (d, J = 5.0 Hz), 55.76, 48.41, 29.30, 28.35, 21.26, 20.87, 18.70, 18.51, 17.55. .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -135.75. 259 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.39 (d, film) 3376, calcd for C.sub.27H.sub.37N.sub.2O.sub.8, J = 7.7 Hz, 1H), 8.28 (d, J = 5.4 Hz, 2960, 517.2544; found, 517.2539 1H), 6.97-6.92 (m, 2H), 1737, 6.76-6.68 (m, 1H), 6.66 (d, J = 1.6 Hz, 1H), 1678, 5.80-5.72 (m, 2H), 5.42 (d, J = 8.1 Hz, 1505, 1H), 4.76-4.65 (m, 1H), 3.91 (s, 3H), 1203, 3.76 (s, 3H), 3.34 (s, 1H), 2.32 (s, 3H), 1042, 2.15-2.02 (m, 4H), 1.52 (d, J = 7.1 Hz, 1004, 971, 3H), 1.07 (d, J = 6.2 Hz, 3H), 736 cm.sup.-1 0.84 (d, J = 6.8 Hz, 3H), 0.74 (d, J = 6.8 Hz, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 172.43, 170.26, 162.95, 160.30, 158.11, 145.71, 143.99, 142.75, 137.16, 124.61, 120.70, 111.72, 109.51, 89.64, 73.51, 56.18, 55.32, 48.52, 29.30, 28.82, 21.43, 21.14, 20.87, 18.83, 18.49, 18.17. 260 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.37 (d, film) 3379, calcd for C.sub.27H.sub.37N.sub.2O.sub.8, J = 7.8 Hz, 1H), 8.28 (d, J = 5.4 Hz, 2960, 517.2544; found, 517.2536 1H), 7.04-6.97 (m, 1H), 6.95 (d, J = 5.4 Hz, 1732, 1H), 6.70 (d, J = 7.5 Hz, 2H), 1674, 5.75 (d, J = 0.7 Hz, 2H), 5.36 (dq, J = 9.3, 1502, 6.2 Hz, 1H), 4.77-4.65 (m, 1H), 1201, 3.91 (s, 3H), 3.78 (s, 3H), 3.07 (dd, J = 9.3, 1043, 6.0 Hz, 1H), 2.30 (s, 3H), 1003, 969, 2.18-2.09 (m, 1H), 2.07 (s, 3H), 1.53 (d, J = 7.1 Hz, 830, 730 cm.sup.-1 3H), 1.06 (d, J = 6.2 Hz, 3H), 0.84 (d, J = 6.8 Hz, 3H), 0.79 (d, J = 6.8 Hz, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 172.47, 170.26, 162.97, 160.31, 157.57, 145.70, 144.04, 142.62, 138.90, 130.02, 128.86, 115.89, 110.88, 109.56, 89.62, 74.11, 56.19, 55.05, 48.48, 29.65, 29.30, 21.09, 20.99, 20.87, 18.71, 18.47, 18.31. 261 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.58 (d, film) 3379, calcd for C.sub.25H.sub.33N.sub.2O.sub.7, J = 7.7 Hz, 1H), 8.32 (d, J = 5.4 Hz, 2961, 473.2282; found, 473.2264 1H), 7.22-7.13 (m, 1H), 7.07 (dd, J = 7.6, 1770, 1.8 Hz, 1H), 7.00 (d, J = 5.6 Hz, 1732, 1H), 6.97-6.80 (m, 2H), 1675, 5.64-5.28 (m, 1H), 4.77-4.57 (m, 1H), 3.91 (s, 1508, 3H), 3.77 (s, 3H), 3.55-3.28 (m, 1H), 1175, 731 cm.sup.-1 2.40 (s, 3H), 2.12 (dq, J = 13.4, 6.7 Hz, 1H), 1.50 (d, J = 7.1 Hz, 3H), 1.08 (d, J = 6.3 Hz, 3H), 0.85 (d, J = 6.8 Hz, 3H), 0.74 (d, J = 6.7 Hz, 3H). 262 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.58 (s, film) 3379, calcd for C.sub.26H.sub.35N.sub.2O.sub.8, 1H), 8.32 (d, J = 5.4 Hz, 1H), 7.00 (d, J = 5.5 Hz, 2960, 503.2388; found, 503.2374 1H), 6.96 (d, J = 8.2 Hz, 1H), 1770, 6.47-6.39 (m, 2H), 5.42 (d, J = 9.2 Hz, 1732, 1H), 4.79-4.61 (m, 1H), 3.91 (s, 1676, 3H), 3.78 (s, 3H), 3.74 (s, 3H), 1505, 3.45-3.16 (m, 1H), 2.40 (s, 3H), 1205, 730 cm.sup.-1 2.13-2.01 (m, 1H), 1.50 (d, J = 7.1 Hz, 3H), 1.07 (d, J = 6.3 Hz, 3H), 0.83 (d, J = 6.7 Hz, 3H), 0.73 (d, J = 6.8 Hz, 3H). 263 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.38 (d, film) 3379, calcd for C.sub.26H.sub.35N.sub.2O.sub.8, J = 7.8 Hz, 1H), 8.27 (d, J = 5.4 Hz, 2961, 503.2388; found, 503.2359 1H), 7.22-7.13 (m, 1H), 7.07 (dd, J = 7.6, 1735, 1.8 Hz, 1H), 6.94 (d, J = 5.4 Hz, 1674, 1H), 6.92-6.75 (m, 2H), 1493, 5.82-5.69 (m, 2H), 5.45 (s, 1H), 4.81-4.59 (m, 1203, 969, 1H), 3.91 (s, 3H), 3.77 (s, 3H), 733 cm.sup.-1 3.53-3.23 (m, 1H), 2.16-2.05 (m, 4H), 1.52 (d, J = 7.1 Hz, 3H), 1.08 (d, J = 6.2 Hz, 3H), 0.85 (d, J = 6.7 Hz, 3H), 0.74 (d, J = 6.8 Hz, 3H). 264 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.38 (d, film) 3379, calcd for C.sub.27H.sub.37N.sub.2O.sub.9, J = 7.8 Hz, 1H), 8.27 (d, J = 5.4 Hz, 2960, 533.2494; found, 533.2488 1H), 7.03-6.84 (m, 2H), 6.43 (d, J = 7.8 Hz, 1734, 2H), 5.74 (d, J = 1.2 Hz, 2H), 1675, 5.46-5.34 (m, 1H), 4.78-4.62 (m, 1505, 1H), 3.90 (s, 3H), 3.78 (s, 3H), 3.74 (s, 1204, 3H), 3.42-2.96 (m, 1H), 1041, 830, 2.15-2.04 (m, 4H), 1.51 (d, J = 7.2 Hz, 3H), 731 cm.sup.-1 1.07 (d, J = 6.2 Hz, 3H), 0.82 (d, J = 6.7 Hz, 3H), 0.73 (d, J = 6.8 Hz, 3H). 265 ESIMS m/z 268.3 ([M + H].sup.+) 266 ESIMS m/z 310.3 ([M + H].sup.+) 267 ESIMS m/z 324.3 ([M + H].sup.+) 268 ESIMS m/z 324.3 ([M + H].sup.+) 269 IR (thin HRMS-ESI (m/z) [M + H].sup.+ film) 2969, calcd for C.sub.17H.sub.28NO.sub.2, 1743, 278.2115; found, 278.2108 1502, 1449, 1365, 1230, 1216, 1203, 1120, 1053, 805 cm.sup.-1 270 IR (thin HRMS-ESI (m/z) [M + H].sup.+ film) 2961, calcd for C.sub.16H.sub.25FNO.sub.2, 2826, 282.1864; found, 282.1877 1739, 1578, 1508, 1466, 1368, 1253, 1235, 1197, 1166, 1094, 1044, 786, 754 cm.sup.-1 271 IR (thin HRMS-ESI (m/z) [M + H].sup.+ film) 2959, calcd for C.sub.15H.sub.23FNO.sub.2, 2851, 268.1707; found, 268.1718 1739, 1583, 1491, 1454, 1248, 1231, 1197, 1120, 1051, 761 cm.sup.-1 272 IR (thin HRMS-ESI (m/z) [M + H].sup.+ film) 2959, calcd for C.sub.16H.sub.25FNO.sub.2, 2873, 282.1864; found, 282.1869 1737, 1587, 1530, 1498, 1457, 1284, 1238, 1190, 1114, 1047, 873, 813 cm.sup.-1 273 IR (thin HRMS-ESI (m/z) [M + H].sup.+ film) 2870, calcd for C.sub.17H.sub.28NO.sub.2, 1742, 278.2115; found, 278.2119 1594, 1502, 1454, 1377, 1251, 1226, 1199, 1118, 1048, 887, 818 cm.sup.-1 274 IR (thin HRMS-ESI (m/z) [M + H].sup.+ film) 2871, calcd for C.sub.17H.sub.28NO.sub.2, 1740, 278.2115; found, 278.2110 1588, 1407, 1455, 1384, 1252, 1239, 1200, 1117, 1044, 783 cm.sup.-1 275 IR (thin HRMS-ESI (m/z) [M + H].sup.+ film) 2871, calcd for C.sub.16H.sub.26NO.sub.2, 1738, 264.1958; found, 264.1953 1586, 1505, 1455, 1244, 1196, 1162, 1119, 1053, 754 cm.sup.-1 276 IR (thin HRMS-ESI (m/z) [M + H].sup.+ film) 2961, calcd for C.sub.15H.sub.22F.sub.2NO.sub.2, 2872, 286.1613; found, 286.1628 1754, 1740, 1602, 1501, 1244, 1116, 1082, 967, 846 cm.sup.-1 277 IR (thin HRMS-ESI (m/z) [M + H].sup.+ film) 2960, calcd for C.sub.16H.sub.25FNO.sub.2, 1757, 282.1864; found, 282.1871 1508, 1458, 1269, 1236, 1212, 1124, 1050, 853, 819 cm.sup.-1 278 IR (thin film) 2967, 2873,

1737, 1589, 1476, 1382, 1251, 1229, 1121, 1107, 1043, 871, 845, 824 cm.sup.-1 279 IR (thin HRMS-ESI (m/z) [M + H].sup.+ film) 2963, calcd for C.sub.15H.sub.22F.sub.2NO.sub.2, 1740, 286.1613; found, 286.1637 1602, 1501, 1458, 1234, 1207, 1172, 1113, 964, 846 cm.sup.-1 280 IR (thin HRMS-ESI (m/z) [M + H].sup.+ film) 2961, calcd for C.sub.16H.sub.25FNO.sub.2, 1740, 282.1864; found, 282.1878 1506, 1456, 1235, 1207, 1115, 939 cm.sup.-1 281 IR (thin HRMS-ESI (m/z) [M + H].sup.+ film) 2962, calcd for C.sub.15H.sub.22Cl.sub.2NO.sub.2, 1739, 318.1022; found, 318.1022 1470, 1381, 1233, 1192, 1109, 1044, 1007, 806 cm.sup.-1 282 IR (thin film) 3391, 2959, 2875, 1736, 1488, 1231, 1196, 1114, 1035 cm.sup.-1 283 HRMS-ESI (m/z) [M + H].sup.+ calcd for C.sub.16H.sub.23F.sub.3NO.sub.3, 334.1625; found, 334.1616 284 IR (thin film) 2973, 1738, 1509, 1237, 1117, 831 cm.sup.-1 285 HRMS-ESI (m/z) [M + H].sup.+ calcd for C.sub.18H.sub.30NO.sub.3, 308.2226; found, 308.2074 286 HRMS-ESI (m/z) [M + Na].sup.+ calcd for C.sub.16H.sub.25NO.sub.3Na, 302.1727; found, 302.1723 287 288 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.04 (dd, film) 3367, calcd for C.sub.20H.sub.30FNNaO.sub.4, J = 8.5, 5.9 Hz, 1H), 6.87 (ddt, J = 11.6, 2964, 390.2051; found, 390.2053 8.3, 4.1 Hz, 2H), 5.40 (dq, J = 8.3, 6.3 Hz, 1713, 1H), 5.02 (s, 1H), 3.93-3.85 (m, 1498, 2H), 3.02 (t, J = 7.7 Hz, 1H), 2.31 (s, 1366, 3H), 2.07 (h, J = 6.8 Hz, 1H), 1.46 (s, 1164, 9H), 1.04 (d, J = 6.3 Hz, 3H), 0.91 (d, J = 6.7 Hz, 1052, 954, 3H), 0.77 (d, J = 6.8 Hz, 3H). 862 cm.sup.-1 .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 169.85, 160.98 (d, J = 244.6 Hz), 155.63, 139.89 (d, J = 8.0 Hz), 133.68 (d, J = 2.8 Hz), 129.24 (d, J = 7.3 Hz), 117.01 (d, J = 20.5 Hz), 112.37 (d, J = 20.8 Hz), 79.96, 73.61, 49.56, 42.78, 29.85, 28.33, 20.96, 20.78, 19.55, 17.64. .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.37. 289 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.04 (dd, film) 2964, calcd for C.sub.23H.sub.36FNNaO.sub.4, J = 8.6, 6.0 Hz, 1H), 6.87 (qd, J = 9.3, 1712, 432.2521; found, 432.2521 8.4, 2.8 Hz, 2H), 5.33 (dq, J = 9.5, 6.2 Hz, 1498, 1H), 4.97 (d, J = 9.4 Hz, 1H), 1366, 4.24 (dd, J = 9.3, 4.4 Hz, 1H), 3.09 (dd, J = 9.5, 1158, 5.7 Hz, 1H), 2.33 (s, 3H), 1049, 863 cm.sup.-1 2.26-2.07 (m, 2H), 1.46 (s, 9H), 1.02 (d, J = 6.2 Hz, 3H), 1.00 (d, J = 6.9 Hz, 3H), 0.88 (d, J = 6.9 Hz, 3H), 0.83 (d, J = 6.8 Hz, 3H), 0.80 (d, J = 6.9 Hz, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 171.82, 160.99 (d, J = 244.4 Hz), 155.66, 139.90 (d, J = 7.6 Hz), 133.39 (d, J = 2.7 Hz), 129.26 (d, J = 7.4 Hz), 117.04 (d, J = 20.5 Hz), 112.37 (d, J = 20.6 Hz), 79.70, 73.46, 58.88, 49.31, 31.26, 29.27, 28.34, 20.91, 19.38, 18.39, 17.03. .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.33. 290 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.04 (dd, film) 2964, calcd for C.sub.24H.sub.38FNNaO.sub.4, J = 8.6, 5.9 Hz, 1H), 6.93-6.81 (m, 1712, 446.2677; found, 446.2681 2H), 5.33 (dq, J = 9.5, 6.2 Hz, 1H), 1498, 4.96 (d, J = 9.3 Hz, 1H), 4.28 (dd, J = 9.3, 1366, 4.5 Hz, 1H), 3.10 (dd, J = 9.6, 5.5 Hz, 1158, 1H), 2.33 (s, 3H), 2.14 (dt, J = 13.5, 6.7 Hz, 1049, 863 cm.sup.-1 1H), 1.99-1.83 (m, 1H), 1.54-1.32 (m, 10H), 1.21-1.08 (m, 1H), 1.02 (d, J = 6.2 Hz, 3H), 0.97 (d, J = 6.8 Hz, 3H), 0.91 (t, J = 7.4 Hz, 3H), 0.82 (d, J = 6.9 Hz, 3H), 0.80 (d, J = 6.9 Hz, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 171.79, 161.00 (d, J = 244.4 Hz), 155.59, 139.90 (d, J = 7.3 Hz), 133.33 (d, J = 2.9 Hz), 129.28 (d, J = 7.6 Hz), 117.05 (d, J = 20.5 Hz), 112.37 (d, J = 20.7 Hz), 79.69, 73.41, 58.61, 49.35, 37.97, 29.19, 28.35, 24.40, 20.92, 18.45, 18.21, 15.71, 11.56. .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.32. 291 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.05 (dd, film) 3365, calcd for C.sub.24H.sub.38FNNaO.sub.4, J = 8.5, 5.9 Hz, 1H), 6.93-6.82 (m, 2960, 446.2677; found, 446.2675 2H), 5.31 (dq, J = 9.2, 6.2 Hz, 1H), 1714, 4.85 (d, J = 8.8 Hz, 1H), 4.29 (td, J = 9.1, 4.8 Hz, 1499, 1H), 3.08 (dd, J = 9.2, 6.1 Hz, 1H), 1367, 2.33 (s, 3H), 2.12 (h, J = 6.7 Hz, 1H), 1165, 1.70 (dq, J = 13.1, 6.8 Hz, 1H), 1049, 863 cm.sup.-1 1.58 (ddd, J = 13.5, 8.4, 5.1 Hz, 1H), 1.52-1.36 (m, 10H), 1.03 (d, J = 6.2 Hz, 3H), 0.95 (dd, J = 6.6, 3.0 Hz, 6H), 0.85 (d, J = 6.8 Hz, 3H), 0.78 (d, J = 6.8 Hz, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 172.88, 160.98 (d, J = 244.5 Hz), 155.31, 139.86 (d, J = 7.3 Hz), 133.62 (d, J = 2.9 Hz), 129.25 (d, J = 8.4 Hz), 116.99 (d, J = 20.5 Hz), 112.37 (d, J = 20.6 Hz), 79.73, 73.45, 52.55, 49.36, 41.84, 29.51, 28.33, 24.82, 23.05, 21.82, 20.95, 18.75, 18.09. .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.42. 292 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 7.04 (d, J = 7.6 Hz, film) 3357, calcd for C.sub.22H.sub.35NO.sub.4Na, 1H), 6.92 (dd, J = 7.7, 1.7 Hz, 2963, 400.2458; found, 400.2450 1H), 6.89 (s, 1H), 5.35 (dq, J = 9.4, 6.2 Hz, 2874, 1H), 5.08 (d, J = 7.9 Hz, 1H), 1712, 4.30 (t, J = 7.6 Hz, 1H), 3.09 (dd, J = 9.4, 6.0 Hz, 1501, 1H), 2.29 (s, 3H), 2.28 (s, 3H), 1451, 2.14 (dq, J = 13.5, 6.7 Hz, 1H), 1.45 (s, 9H), 1365, 1.40 (d, J = 7.1 Hz, 3H), 1.04 (d, J = 6.2 Hz, 1160, 1049 cm.sup.-1 3H), 0.84 (d, J = 6.8 Hz, 3H), 0.81 (d, J = 6.9 Hz, 3H). 293 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 7.11 (td, film) 3356, calcd for C.sub.21H.sub.32FNO.sub.4Na, J = 7.9, 5.9 Hz, 1H), 6.99-6.82 (m, 2965, 404.2208; found, 404.2208 2H), 5.36 (dq, J = 9.1, 6.2 Hz, 1H), 1712, 5.05 (d, J = 7.8 Hz, 1H), 4.29 (t, J = 7.5 Hz, 1500, 1H), 3.14 (dd, J = 9.0, 6.4 Hz, 1H), 1455, 2.24 (d, J = 2.3 Hz, 3H), 2.14 (dq, J = 13.4, 1365, 6.7 Hz, 1H), 1.45 (s, 9H), 1.39 (d, J = 7.2 Hz, 1245, 3H), 1.04 (d, J = 6.2 Hz, 3H), 1161, 0.86 (d, J = 6.8 Hz, 3H), 0.79 (d, J = 6.8 Hz, 1045, 820 cm.sup.-1 3H). 294 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. film) 3363, calcd for C.sub.20H.sub.30FNO.sub.4Na, 7.25-7.19 (m, 1H), 7.12 (dtd, J = 22.9, 7.6, 2965, 390.2051; found, 390.2053 1.6 Hz, 2H), 7.03 (ddd, J = 9.7, 8.1, 1.3 Hz, 2933, 1H), 5.43 (dqd, J = 7.5, 6.3, 1.3 Hz, 1712, 1H), 5.06 (d, J = 7.9 Hz, 1H), 1491, 4.39-4.15 (m, 1H), 3.18 (t, J = 7.7 Hz, 1H), 1453, 2.22-2.03 (m, 1H), 1.45 (s, 9H), 1365, 1.38 (d, J = 7.2 Hz, 3H), 1.10 (d, J = 6.3 Hz, 1162, 3H), 1.04-0.86 (m, 3H), 0.77 (d, J = 6.7 Hz, 1052, 757 cm.sup.-1 3H). 295 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 7.12 (dd, film) 3356, calcd for C.sub.21H.sub.32FNO.sub.4Na, J = 8.5, 6.0 Hz, 1H), 6.88-6.75 (m, 2969, 404.2208; found, 404.2204 2H), 5.31 (dq, J = 9.0, 6.3 Hz, 1H), 1712, 5.05 (d, J = 7.9 Hz, 1H), 4.43-4.15 (m, 1H), 1497, 3.10 (t, J = 7.4 Hz, 1H), 2.29 (s, 3H), 1365, 2.12 (h, J = 6.8 Hz, 1H), 1.45 (s, 9H), 1243, 1.38 (d, J = 7.2 Hz, 3H), 1.06 (d, J = 6.3 Hz, 1161, 3H), 0.87 (d, J = 6.7 Hz, 3H), 1051, 731 cm.sup.-1 0.81 (d, J = 6.8 Hz, 3H). 296 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. film) 3356, calcd for C.sub.22H.sub.35NO.sub.4Na, 7.04-6.91 (m, 3H), 5.35 (dq, J = 9.3, 6.3 Hz, 2962, 400.2458; found, 400.2462 1H), 5.07 (s, 1H), 4.29 (t, J = 7.6 Hz, 1713, 1H), 3.08 (dd, J = 9.4, 6.0 Hz, 1H), 1501, 2.29 (s, 3H), 2.29 (s, 3H), 2.12 (dq, J = 13.4, 1451, 6.8 Hz, 1H), 1.45 (s, 9H), 1.39 (d, J = 7.2 Hz, 1365, 3H), 1.03 (d, J = 6.2 Hz, 3H), 1160, 0.84 (d, J = 6.7 Hz, 3H), 0.80 (d, J = 6.9 Hz, 1049, 732 cm.sup.-1 3H). 297 IR (thin HRMS-ESI (m/z) .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. film) 3352, [M + NH4].sup.+ calcd for 7.07-7.01 (m, 2H), 6.95 (dd, J = 7.0, 2.3 Hz, 2964, C.sub.22H.sub.35NO.sub.4NH.sub.4, 395.2904; 1H), 5.37 (dq, J = 9.2, 6.3 Hz, 1H), 1712, found, 395.2889 5.08 (s, 1H), 4.30 (t, J = 7.8 Hz, 1H), 1499, 3.23 (dd, J = 9.3, 6.0 Hz, 1H), 2.30 (s, 3H), 1452, 2.24 (s, 3H), 2.13 (dq, J = 13.4, 6.7 Hz, 1365, 1H), 1.45 (s, 9H), 1.40 (d, J = 7.1 Hz, 1160, 3H), 1.03 (d, J = 6.2 Hz, 3H), 0.84 (d, J = 6.8 Hz, 1050, 731 cm.sup.-1 3H), 0.79 (d, J = 6.9 Hz, 3H). 298 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. film) 3359, calcd for C.sub.21H.sub.33NO.sub.4Na, 7.20-7.06 (m, 4H), 5.37 (dq, J = 9.3, 6.2 Hz, 2965, 386.2302; found, 386.2301 1H), 5.07 (d, J = 7.8 Hz, 1H), 4.29 (t, J = 7.2 Hz, 2875, 1H), 3.13 (dd, J = 9.2, 6.1 Hz, 1714, 1H), 2.34 (s, 3H), 2.15 (dq, J = 13.4, 6.8 Hz, 1161, 1054 cm.sup.-1 1H), 1.45 (s, 9H), 1.39 (d, J = 7.2 Hz, 3H), 1.04 (d, J = 6.2 Hz, 3H), 0.86 (d, J = 6.8 Hz, 3H), 0.81 (d, J = 6.8 Hz, 3H). 299 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 7.10 (td, film) 3365, calcd for C.sub.20H.sub.29F.sub.2NO.sub.4Na, J = 8.4, 6.4 Hz, 1H), 6.93-6.74 (m, 2966, 408.1957; found, 408.1955 2H), 5.39 (tt, J = 7.0, 5.5 Hz, 1H), 1712, 5.04 (d, J = 7.9 Hz, 1H), 4.26 (t, J = 7.6 Hz, 1503, 1H), 3.13 (t, J = 7.7 Hz, 1H), 2.10 (h, J = 6.8 Hz, 1454, 1H), 1.45 (s, 9H), 1.37 (d, J = 7.2 Hz, 1366, 3H), 1.09 (d, J = 6.3 Hz, 3H), 1165, 0.91 (d, J = 6.8 Hz, 3H), 0.75 (d, J = 6.7 Hz, 1053, 966, 3H). 849 cm.sup.-1 300 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 7.00 (t, J = 7.7 Hz, film) 2969, calcd for C.sub.21H.sub.32FNO.sub.4Na, 1H), 6.90 (dd, J = 7.9, 1.7 Hz, 1716, 404.2208; found, 404.2202 1H), 6.87-6.74 (m, 1H), 5.40 (tt, J = 6.9,

1506, 5.5 Hz, 1H), 5.07 (d, J = 8.1 Hz, 1456, 1H), 4.33-4.16 (m, 1H), 3.11 (t, J = 7.7 Hz, 1365, 1H), 2.33 (s, 3H), 2.10 (h, J = 6.8 Hz, 1164, 1053 cm.sup.-1 1H), 1.45 (s, 9H), 1.38 (d, J = 7.2 Hz, 3H), 1.09 (d, J = 6.3 Hz, 3H), 0.90 (d, J = 6.7 Hz, 3H), 0.76 (d, J = 6.7 Hz, 3H). 301 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 7.42 (d, J = 2.3 Hz, film) 3358, calcd for 1H), 7.23 (dd, J = 8.5, 2.2 Hz, 2966, C.sub.20H.sub.29Cl.sub.2NO.sub.4Na, 1H), 7.13 (d, J = 8.5 Hz, 1H), 1712, 440.1366; found, 440.1366 5.47-5.25 (m, 1H), 5.03 (d, J = 7.6 Hz, 1H), 1500, 4.28 (d, J = 7.7 Hz, 1H), 3.51 (s, 1H), 1474, 2.24-1.99 (m, 1H), 1.45 (s, 9H), 1453, 1.39 (d, J = 7.2 Hz, 3H), 1.08 (d, J = 6.4 Hz, 1365, 3H), 0.92 (d, J = 6.8 Hz, 3H), 0.77 (d, J = 6.8 Hz, 1162, 1045 cm.sup.-1 3H). 302 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. film) 3346, calcd for C.sub.20H.sub.29F.sub.2NO.sub.4Na, 7.27 (m, 1H), 6.90-6.82 (m, 1H), 2975, 408.1957; found, 408.1956 6.82-6.75 (m, 1H), 5.54-5.30 (m, 1H), 1710, 5.01 (d, J = 8.6 Hz, 1H), 4.35-4.18 (m, 1502, 1H), 2.84 (dd, J = 9.1, 5.2 Hz, 1H), 1366, 2.09-1.87 (m, 1H), 1.44 (s, 9H), 1.24 (d, J = 7.3 Hz, 1249, 3H), 1.10 (d, J = 6.3 Hz, 3H), 1163, 0.97 (d, J = 6.5 Hz, 3H), 0.72 (d, J = 6.8 Hz, 1064, 965 3H). 847 cm.sup.-1 303 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 7.17 (t, J = 7.8 Hz, film) 3364, calcd for C.sub.21H.sub.32FNO.sub.4Na, 1H), 6.90 (d, J = 7.6 Hz, 1H), 2974, 404.2208; found, 404.2206 6.84 (dd, J = 11.0, 1.8 Hz, 1H), 2932, 5.44-5.38 (m, 1H), 5.04 (d, J = 7.4 Hz, 1H), 1714 4.46-4.15 (m, 1H) 2.83 (dd, J = 9.0, 1506, 5.1 Hz, 1H), 2.33 (d, J = 3.0 Hz, 3H), 1454, 2.11-1.97 (m, 1H), 1.44 (s, 9H), 1336, 1.22 (d, J = 7.2 Hz, 3H), 1.10 (d, J = 6.3 Hz, 1167, 1065 cm.sup.-1 3H), 0.97 (d, J = 6.6 Hz, 3H), 0.73 (d, J = 6.9 Hz, 3H). 304 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 7.40 (d, J = 2.2 Hz, film) 3353, calcd for 1H), 7.36 (d, J = 8.5 Hz, 1H), 2975, C.sub.20H.sub.29Cl.sub.2NO.sub.4Na, 7.24-7.06 (m, 1H), 5.62-5.20 (m, 1710, 440.1366; found, 440.1360 1H), 5.02 (d, J = 8.1 Hz, 1H), 1475, 4.46-4.13 (m, 1H), 3.13 (dd, J = 9.6, 4.6 Hz, 1366, 1H), 2.20-1.92 (m, 1H), 1.44 (s, 9H), 1163, 1.37-1.26 (m, 3H), 1.06 (d, J = 6.3 Hz, 1111, 3H), 1.01 (d, J = 6.6 Hz, 3H), 0.70 (d, J = 6.8 Hz, 1020, 863, 3H). 809 cm.sup.-1 305 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 6.74 (d, J = 7.9 Hz, film) 3375, calcd for C.sub.21H.sub.31NO.sub.6Na, 1H), 6.60 (d, J = 1.8 Hz, 1H), 2969, 416.2044; found, 416.2040 6.54 (dd, J = 8.0, 1.7 Hz, 1H), 5.94 (s, 1711, 2H), 5.31 (dq, J = 8.8, 6.3 Hz, 1H), 1504, 5.07 (d J = 7.8 Hz, 1H), 4.33-4.20 (m, 1H), 1488, 2.61 (dd, J = 8.8, 6.4 Hz, 1H), 1160, 2.12-1.98 (m, J = 6.8 Hz, 1H), 1.45 (s, 9H), 1038, 731 cm.sup.-1 1.38 (d, J = 7.2 Hz, 3H), 1.08 (d, J = 6.2 Hz, 3H), 0.85 (d, J = 6.7 Hz, 3H), 0.76 (d, J = 6.7 Hz, 3H). 306 IR (thin .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 7.13 (q, J = 8.8 Hz, film) 3361, 4H), 5.37 (dq, J = 8.7, 6.3 Hz, 2970, 1H), 5.04 (d, J = 8.0 Hz, 1H), 1715, 4.37-4.22 (m, 1H), 2.72 (dd, J = 8.6, 6.6 Hz, 1366, 1H), 2.10 (h, J = 6.7 Hz, 1H), 1.45 (s, 1262, 9H), 1.37 (d, J = 7.2 Hz, 3H), 1.07 (d, J = 6.3 Hz, 1218, 1165 cm.sup.-1 3H), 0.87 (d, J = 6.8 Hz, 3H), 0.75 (d, J = 6.7 Hz, 3H). .sup.19F NMR (471 MHz, CDCl.sub.3) .delta. -57.9. 307 IR (thin .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. film) 3363, 7.06-6.91 (m, 2H), 6.90-6.75 (m, 2H), 2976, 5.35 (dq, J = 8.9, 6.3 Hz, 1H), 5.08 (d, J = 8.0 Hz, 2933, 1H), 4.52 (hept, J = 6.1 Hz, 1H), 2875, 4.36-4.22 (m, 1H), 2.63 (dd, J = 9.0, 1712, 6.1 Hz, 1H), 2.14-2.00 (m, 1H), 1508, 1.45 (s, 9H), 1.38 (d, J = 7.2 Hz, 3H), 1238, 1.33 (d, J = 6.1 Hz, 6H), 1.06 (d, J = 6.2 Hz, 1165, 1050 cm.sup.-1 3H), 0.84 (d, J = 6.8 Hz, 3H), 0.75 (d, J = 6.7 Hz, 3H). .sup.13C NMR (126 MHz, CDCl.sub.3) .delta. 172.8, 156.6, 155.0, 130.6, 130.3, 115.2, 79.7, 72.7, 69.7, 60.4, 55.8, 49.5, 28.3, 28.2, 22.1, 21.4, 18.9, 18.3, 18.0. 308 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. film) 3357, calcd for C.sub.23H.sub.37NO.sub.5Na, 7.23-7.11 (m, 1H), 7.06 (dd, J = 7.8, 1.8 Hz, 2976, 430.2569; found, 430.2431 1H), 6.92-6.78 (m, 2H), 5.42 (s, 1H), 2933, 5.13 (d, J = 7.7 Hz, 1H), 4.56 (hept, J = 6.1 Hz, 2874, 1H), 4.30 (t, J = 7.5 Hz, 1H), 1712, 3.44 (s, 1H), 2.12 (h, J = 6.7 Hz, 1H), 1489, 1.45 (s, 9H), 1.40 (d, J = 7.2 Hz, 3H), 1238, 1.39-1.26 (m, 6H), 1.04 (d, J = 6.2 Hz, 1160, 3H), 0.83 (d, J = 6.8 Hz, 3H), 0.76 (d, J = 6.8 Hz, 1050, 732 cm.sup.-1 3H). 309 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. film) 3361, calcd for C.sub.21H.sub.33NO.sub.5Na, 7.09-6.90 (m, 2H), 6.90-6.77 (m, 2H), 2962, 402.2251; found, 402.2221 5.35 (dq, J = 8.9, 6.3 Hz, 1H), 5.07 (s, 1H), 1713, 4.28 (t, J = 7.6 Hz, 1H), 3.80 (s, 3H), 1512, 2.64 (dd, J = 8.9, 6.2 Hz, 1H), 2.07 (h, J = 6.7 Hz, 1246, 1H), 1.45 (s, 9H), 1.38 (d, J = 7.2 Hz, 1165, 1050 cm.sup.-1 3H), 1.06 (d, J = 6.2 Hz, 3H), 0.84 (d, J = 6.8 Hz, 3H), 0.75 (d, J = 6.8 Hz, 3H). 310 ESIMS m/z 400 .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. ([M + Na].sup.+) 7.23-7.04 (m, 4H), 5.38 (dq, J = 9.6, 6.1 Hz, 1H), 5.09 (s, 1H), 4.41-4.22 (m, 1H), 3.32-3.07 (m, 1H), 2.34 (d, J = 2.6 Hz, 3H), 1.89 (dtd, J = 12.5, 6.2, 5.6, 3.2 Hz, 1H), 1.54-1.33 (m, 12H), 1.32-1.20 (m, 1H), 1.14-0.69 (m, 10H). 311 ESIMS m/z 392 ([M + H].sup.+) .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.20-7.03 (m, 4H), 5.41 (dq, J = 8.3, 6.2 Hz, 1H), 5.06 (s, 1H), 4.27 (s, 1H), 3.30 (t, J = 7.6 Hz, 1H), 2.33 (s, 3H), 1.72-1.58 (m, 1H), 1.44 (s, 10H), 1.36 (dd, J = 10.9, 7.2 Hz, 5H), 1.08 (d, J = 6.3 Hz, 4H), 0.93 (t, J = 7.4 Hz, 3H), 0.78 (t, J = 7.3 Hz, 3H). 312 .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 6.67 (d, J = 9.3 Hz, 2H), 5.54 (ddt, J = 8.1, 6.3, 2.0 Hz, 1H), 5.04 (s, 1H), 4.27 (d, J = 8.5 Hz, 1H), 3.17 (t, J = 7.7 Hz, 1H), 2.30-2.15 (m, 1H), 1.45 (s, 9H), 1.37 (d, J = 7.3 Hz, 3H), 1.12 (dt, J = 6.3, 1.2 Hz, 3H), 0.95 (d, J = 6.6 Hz, 3H), 0.77 (dt, J = 6.8, 1.4 Hz, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -103.51, -108.05, -110.09. 313 .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.09 (dtt, J = 8.3, 5.6, 2.7 Hz, 3H), 5.47-5.32 (m, 1H), 5.03 (s, 1H), 4.26 (s, 1H), 3.13 (t, J = 7.7 Hz, 1H), 2.10 (q, J = 6.8 Hz, 1H), 1.45 (s, 9H), 1.37 (d, J = 7.2 Hz, 3H), 1.09 (d, J = 6.3 Hz, 3H), 0.99-0.85 (m, 3H), 0.75 (d, J = 6.8 Hz, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -112.35. 314 .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.23 (dd, J = 8.4, 1.2 Hz, 1H), 7.16 (td, J = 8.0, 5.6 Hz, 1H), 6.96 (ddd, J = 10.9, 8.1, 1.5 Hz, 1H), 5.58 (ddq, J = 12.5, 9.1, 3.1 Hz, 1H), 5.07 (s, 1H), 4.30 (d, J = 8.5 Hz, 1H), 3.60-3.48 (m, 1H), 2.24 (dqd, J = 13.7, 6.8, 2.1 Hz, 1H), 1.45 (s, 9H), 1.40 (d, J = 7.2 Hz, 3H), 1.08 (dd, J = 6.3, 1.8 Hz, 3H), 0.99 (d, J = 6.8 Hz, 3H), 0.78 (dd, J = 6.8, 2.8 Hz, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -105.00 315 .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.17 (t, J = 7.8 Hz, 1H), 7.05 (d, J = 7.6 Hz, 1H), 6.89 (s, 2H), 5.45-5.32 (m, 1H), 5.08 (s, 1H), 4.28 (s, 1H), 2.65 (dd, J = 8.9, 6.2 Hz, 1H), 2.33 (s, 3H), 2.14-2.04 (m, 1H), 1.45 (s, 9H), 1.39 (d, J = 7.3 Hz, 3H), 1.07 (d, J = 6.2 Hz, 3H), 0.85 (d, J = 6.8 Hz, 3H), 0.76 (d, J = 6.8 Hz, 3H). 316 ESIMS m/z 386 ([M + H].sup.+) .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.00 (td, J = 9.1, 4.7 Hz, 1H), 6.88 (dddd, J = 24.6, 8.9, 6.3, 3.3 Hz, 2H), 5.49-5.28 (m, 1H), 5.04 (s, 1H), 4.26 (d, J = 9.3 Hz, 1H), 3.15 (t, J = 7.7 Hz, 1H), 2.09 (h, J = 6.9 Hz, 1H), 1.45 (s, 9H), 1.37 (d, J = 7.3 Hz, 3H), 1.12 (d, J = 6.3 Hz, 3H), 0.94 (d, J = 6.7 Hz, 3H), 0.78 (d, J = 6.7 Hz, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -118.45--122.20 (m). 317 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. film) 3374, calcd for C.sub.22H.sub.28FN.sub.2O.sub.5, 12.06-12.02 (m, 1H), 8.47 (t, J = 5.8 Hz, 1H), 2961, 419.1977; found, 419.1976 7.99 (d, J = 5.3 Hz, 1H), 7.05 (dd, J = 8.3, 1740, 5.9 Hz, 1H), 6.90-6.81 (m, 3H), 1650, 5.45 (dq, J = 8.2, 6.3 Hz, 1H), 4.19 (d, J = 5.7 Hz, 1533, 2H), 3.95 (s, 3H), 3.04 (t, J = 7.7 Hz, 1497, 1H), 2.30 (s, 3H), 2.08 (h, J = 6.8 Hz, 1437, 1H), 1.09 (d, J = 6.3 Hz, 3H), 1262, 0.93 (d, J = 6.7 Hz, 3H), 0.77 (d, J = 6.8 Hz, 1240, 3H). 1215, .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 169.35, 1188, 801, 168.66, 160.95 (d, J = 244.4 Hz), 729 cm.sup.-1 155.42, 148.73, 140.59, 139.90 (d, J = 7.5 Hz), 133.63 (d, J = 3.3 Hz), 130.43, 129.20 (d, J = 6.9 Hz), 116.98 (d, J = 20.5 Hz), 112.35 (d, J = 20.7 Hz), 109.57, 74.06, 56.09, 49.55, 41.17, 29.95, 20.95, 20.80, 19.71, 17.46. .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.31. 318 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 12.16 (s, film) 3371, calcd for C.sub.25H.sub.34FN.sub.2O.sub.5, 1H), 8.43 (d, J = 9.5 Hz, 1H), 7.99 (d, J = 5.2 Hz, 2963, 461.2466; found, 461.2453 1H), 7.03 (dd, J = 8.7, 5.9 Hz, 1731, 1H), 6.89 (d, J = 5.2 Hz, 1H), 6.83 (td, J = 8.4, 1651, 2.9 Hz, 1H), 6.77 (dd, J = 9.9, 2.8 Hz, 1527, 1H), 5.37 (dq, J = 9.1, 6.1 Hz, 1H), 1262, 4.66 (dd, J = 9.5, 4.9 Hz, 1H), 3.96 (s, 1240, 730 cm.sup.-1 3H), 3.09 (dd, J = 9.2, 6.1 Hz, 1H), 2.42-2.29 (m, 1H), 2.27 (s, 3H), 2.20-2.06 (m, 1H), 1.07 (d, J = 6.2 Hz, 3H), 1.06 (d, J = 6.9 Hz, 3H), 1.01 (d, J = 6.9 Hz, 3H), 0.82 (d, J = 6.8 Hz, 3H), 0.76 (d, J = 6.9 Hz, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 170.53, 169.10, 160.93 (d, J = 244.6 Hz), 155.43, 148.78, 140.48, 139.88 (d, J = 7.3 Hz), 133.35 (d, J = 3.3 Hz), 130.52, 129.15 (d, J = 7.9 Hz), 116.98 (d, J = 20.5 Hz), 112.31 (d, J = 20.6 Hz), 109.50, 73.81, 57.39, 56.10, 49.30, 31.34, 29.46, 20.88, 19.48, 18.63, 18.11, 17.43. .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.29. 319 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 12.17 (s, film) 3374, calcd for C.sub.26H.sub.36FN.sub.2O.sub.5, 1H), 8.42 (d, J = 9.5 Hz, 1H), 7.98 (d, J = 5.2 Hz, 2963, 475.2603; found, 475.2599 1H), 7.03 (dd, J = 8.7, 5.9 Hz, 1731, 1H), 6.89 (d, J = 5.3 Hz, 1H), 6.83 (td, J = 8.4, 1651, 2.9 Hz, 1H), 6.77 (dd, J = 9.9, 2.8 Hz, 1526, 1H), 5.37 (dq, J = 9.2, 6.2 Hz, 1H), 1261, 4.71 (dd, J = 9.5, 4.9 Hz, 1H), 3.96 (s, 1240, 3H), 3.09 (dd, J = 9.3, 6.0 Hz, 1H), 1046, 800, 2.27 (s, 3H), 2.19-2.03 (m, 2H), 1.54 (dddd, 730 cm.sup.-1 J = 14.9, 11.4, 6.8, 4.0 Hz, 1H), 1.28 (tdd, J = 14.3, 9.8, 7.3 Hz, 1H), 1.07 (d, J = 6.2 Hz, 3H), 1.04 (d, J = 6.8 Hz, 3H), 1.01-0.87 (m, 3H), 0.81 (d, J = 6.8 Hz, 3H), 0.76 (d, J = 6.9 Hz, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 170.48, 168.99, 160.93 (d, J = 244.4 Hz), 155.43, 148.77, 140.47, 139.89 (d, J = 7.3 Hz), 133.30 (d, J = 3.3 Hz), 130.53,

129.16 (d, J = 7.8 Hz), 116.98 (d, J = 20.5 Hz), 112.30 (d, J = 20.6 Hz), 109.49, 73.77, 56.98, 56.10, 49.29, 37.88, 29.40, 24.69, 20.88, 18.48, 18.15, 15.83, 11.48. .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.28. 320 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 12.15 (s, film) 3367, calcd for C.sub.26H.sub.36FN.sub.2O.sub.5, 1H), 8.28 (d, J = 9.0 Hz, 1H), 7.98 (d, J = 5.2 Hz, 2959, 475.2603; found, 475.2600 1H), 7.04 (dd, J = 8.7, 5.9 Hz, 1733, 1H), 6.89 (d, J = 5.2 Hz, 1H), 6.83 (td, J = 8.4, 1650, 2.9 Hz, 1H), 6.77 (dd, J = 9.9, 2.8 Hz, 1529, 1H), 5.35 (dq, J = 8.8, 6.2 Hz, 1H), 1263, 4.79-4.68 (m, 1H), 3.95 (s, 3H), 1244, 3.07 (dd, J = 8.8, 6.6 Hz, 1H), 2.27 (s, 3H), 1049, 800, 2.08 (h, J = 6.8 Hz, 1H), 1.80-1.66 (m, 731 cm.sup.-1 2H), 1.08 (d, J = 6.2 Hz, 3H), 1.05-0.86 (m, 7H), 0.84 (d, J = 6.7 Hz, 3H), 0.75 (d, J = 6.8 Hz, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 171.49, 168.88, 160.90 (d, J = 244.3 Hz), 155.43, 148.80, 140.41, 139.83 (d, J = 7.3 Hz), 133.54 (d, J = 3.3 Hz), 130.45, 129.10 (d, J = 7.1 Hz), 116.91 (d, J = 20.4 Hz), 112.28 (d, J = 20.7 Hz), 109.48, 73.83, 56.08, 50.94, 49.28, 41.40, 29.68, 24.91, 23.00, 21.70, 20.89, 18.98, 17.74. .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.37. 321 IR (thin ESIMS m/z 429.2 .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 12.15 (s, film) 3370, ([M + H].sup.+) 1H), 8.50 (d, J = 7.9 Hz, 1H), 8.00 (d, J = 5.2 Hz, 2959, 1H), 7.02 (d, J = 7.6 Hz, 1H), 2873, 6.95-6.86 (m, 3H), 5.39 (dq, J = 9.3, 1731, 6.2 Hz, 1H), 4.81-4.60 (m, 1H), 1648, 3.95 (s, 3H), 3.20-2.96 (m, 1H), 2.30 (s, 1576, 3H), 2.27 (s, 3H), 2.14 (dq, J = 13.4, 6.7 Hz, 1526, 1H), 1.57 (d, J = 7.2 Hz, 3H), 1480, 1.07 (d, J = 6.2 Hz, 3H), 0.84 (d, J = 6.8 Hz, 1450, 3H), 0.81 (d, J = 6.8 Hz, 3H). 1325, 1280, 1262, 1241, 1149, 1046, 953, 800, 730 cm.sup.-1 322 IR (thin ESIMS m/z 433.2 .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 12.12 (s, film) 3370, ([M + H].sup.+) 1H), 8.48 (d, J = 7.9 Hz, 1H), 8.00 (d, J = 5.2 Hz, 2962, 1H), 7.12 (td, J = 8.0, 5.9 Hz, 2875, 1H), 6.94-6.85 (m, 3H), 5.40 (dq, J = 9.0, 1734, 6.2 Hz, 1H), 4.70 (p, J = 7.3 Hz, 1649, 1H), 3.95 (s, 3H), 3.15 (t, J = 7.7 Hz, 1576, 1H), 2.22 (d, J = 2.4 Hz, 3H), 2.14 (h, J = 6.8 Hz, 1527, 1H), 1.56 (d, J = 7.2 Hz, 3H), 1480, 1.08 (d, J = 6.2 Hz, 3H), 0.86 (d, J = 6.8 Hz, 1453, 3H), 0.79 (d, J = 6.9 Hz, 3H). 1324, 1280, 1263, 1241, 1163, 1043, 786, 732 cm.sup.-1 323 IR (thin ESIMS m/z 419.2 .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 12.15 (s, film) 3370, ([M + H].sup.+) 1H), 8.49 (d, J = 7.9 Hz, 1H), 8.00 (d, J = 5.2 Hz, 2962, 1H), 7.24-7.18 (m, 1H), 1733, 7.15 (td, J = 7.4, 1.9 Hz, 1H), 7.09 (td, J = 7.5, 1648, 1.3 Hz, 1H), 7.00 (ddd, J = 10.3, 1576, 8.2, 1.2 Hz, 1H), 6.88 (d, J = 5.2 Hz, 1527, 1H), 5.47 (dqd, J = 7.6, 6.4, 1.2 Hz, 1480, 1H), 4.73-4.62 (m, 1H), 3.95 (s, 3H), 1452, 3.20 (t, J = 7.7 Hz, 1H), 2.18-2.08 (m, 1280, 1H), 1.55 (d, J = 7.3 Hz, 3H), 1.13 (d, J = 6.3 Hz, 1262, 3H), 0.92 (d, J = 6.8 Hz, 3H), 1241, 0.77 (d, J = 6.7 Hz, 3H). 1216, 1148, 1049, 849, 800, 757, 730 cm.sup.-1 324 IR (thin ESIMS m/z 433.2 .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 12.12 (s, film) 3370, ([M + H].sup.+) 1H), 8.46 (d, J = 8.0 Hz, 1H), 7.99 (d, J = 5.2 Hz, 2959, 1H), 7.07 (dd, J = 8.3, 6.2 Hz, 1731, 1H), 6.88 (d, J = 5.2 Hz, 1H), 1648, 6.84-6.76 (m, 2H), 5.36 (dq, J = 8.7, 6.2 Hz, 1576, 1H), 4.75-4.61 (m, 1H), 3.95 (s, 3H), 1526, 3.11 (t, J = 7.9 Hz, 1H), 2.27 (s, 3H), 1480, 2.11 (h, J = 6.7 Hz, 1H), 1.55 (d, J = 7.2 Hz, 1450, 3H), 1.10 (d, J = 6.3 Hz, 3H), 1438, 0.88 (d, J = 6.8 Hz, 3H), 0.80 (d, J = 6.8 Hz, 1280, 3H). 1262, 1241, 1149, 1046, 953, 819, 799, 730 cm.sup.-1 325 IR (thin ESIMS m/z 429.2 .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 12.15 (s, film) 3370, ([M + H].sup.+) 1H), 8.50 (d, J = 7.9 Hz, 1H), 8.00 (d, J = 5.2 Hz, 2961, 1H), 7.02-6.94 (m, 3H), 1733, 6.88 (d, J = 5.2 Hz, 1H), 5.39 (dq, J = 9.2, 1648, 6.2 Hz, 1H), 4.71 (p, J = 7.3 Hz, 1H), 1576, 3.95 (s, 3H), 3.10 (dd, J = 9.3, 6.1 Hz, 1527, 1H), 2.28 (s, 6H), 2.12 (dq, J = 13.4, 6.8 Hz, 1497, 1H), 1.56 (d, J = 7.2 Hz, 3H), 1451, 1.07 (d, J = 6.2 Hz, 3H), 0.84 (d, J = 6.8 Hz, 1280, 3H), 0.80 (d, J = 6.8 Hz, 3H). 1261, 1240, 1148, 1048, 952, 800, 730 cm.sup.-1 326 IR (thin ESIMS m/z 429.2 .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 12.15 (s, film) 3369, ([M + H].sup.+) 1H), 8.51 (d, J = 7.7 Hz, 1H), 8.00 (d, J = 5.2 Hz, 2961, 1H), 7.09-7.00 (m, 2H), 2873, 6.95 (dd, J = 7.4, 1.8 Hz, 1H), 6.88 (d, J = 5.3 Hz, 1732, 1H), 5.41 (dq, J = 9.0, 6.2 Hz, 1648, 1H), 4.76-4.63 (m, 1H), 3.95 (s, 3H), 1576, 3.25 (dd, J = 9.2, 6.1 Hz, 1H), 2.28 (s, 1526, 3H), 2.23 (s, 3H), 2.18-2.08 (m, 1H), 1480, 1.57 (d, J = 7.2 Hz, 3H), 1.06 (d, J = 6.3 Hz, 1451, 3H), 0.84 (d, J = 6.7 Hz, 3H), 1384, 0.79 (d, J = 6.8 Hz, 3H). 1359, 1262, 1241, 1213, 1150, 1045, 849, 800, 779, 729 cm.sup.-1 327 IR (thin ESIMS m/z 415 ([M + H].sup.+) .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 12.15 (d, film) 3369, J = 0.6 Hz, 1H), 8.50 (d, J = 7.9 Hz, 2960, 1H), 8.00 (d, J = 5.2 Hz, 1H), 2932, 7.19-7.06 (m, 4H), 6.88 (d, J = 5.2 Hz, 1H), 2874, 5.41 (dq, J = 9.2, 6.2 Hz, 1H), 1732, 4.76-4.66 (m, 1H), 3.95 (s, 3H), 3.15 (dd, J = 9.2, 1649, 6.2 Hz, 1H), 2.32 (s, 3H), 2.15 (dq, 1527, J = 13.4, 6.7 Hz, 1H), 1.56 (d, J = 7.2 Hz, 1451, 3H), 1.08 (d, J = 6.2 Hz, 3H), 1150, 0.86 (d, J = 6.8 Hz, 3H), 0.81 (d, J = 6.8 Hz, 1053, 731 cm.sup.-1 3H). 328 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 12.14 (d, film) 2964, calcd for C.sub.22H.sub.27F.sub.2N.sub.2O.sub.5, J = 0.6 Hz, 1H), 8.45 (d, J = 7.9 Hz, 1733, 437.1883; found, 437.1879 1H), 7.99 (d, J = 5.2 Hz, 1H), 7.10 (td, J = 8.4, 1714, 6.4 Hz, 1H), 6.88 (d, J = 5.2 Hz, 1652, 1H), 6.86-6.81 (m, 1H), 6.74 (ddd, J = 10.2, 1528, 8.9, 2.6 Hz, 1H), 5.52-5.31 (m, 1503, 1H), 4.79-4.55 (m, 1H), 3.95 (s, 3H), 1280, 3.14 (t, J = 7.7 Hz, 1H), 2.09 (h, J = 6.8 Hz, 1263, 966, 1H), 1.58-1.53 (m, 3H), 1.12 (d, J = 6.3 Hz, 848 cm.sup.-1 3H), 0.93 (d, J = 6.7 Hz, 3H), 0.75 (d, J = 6.7 Hz, 3H). 329 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 12.16 (d, film) 2962, calcd for C.sub.23H.sub.30FN.sub.2O.sub.5, J = 0.7 Hz, 1H), 8.49 (d, J = 8.0 Hz, 1733, 433.2133; found, 433.2129 1H), 8.00 (d, J = 5.2 Hz, 1H), 7.01 (t, J = 7.7 Hz, 1650, 1H), 6.93-6.84 (m, 2H), 1576, 6.83-6.78 (m, 1H), 5.45 (dqd, J = 7.6, 6.3, 1528, 1.2 Hz, 1H), 4.73-4.60 (m, 1H), 1481, 3.95 (s, 3H), 3.14 (t, J = 7.7 Hz, 1H), 2.32 (s, 1450, 3H), 2.10 (h, J = 6.8 Hz, 1H), 1.55 (d, J = 7.2 Hz, 1362, 3H), 1.12 (d, J = 6.3 Hz, 3H), 1327, 1.01-0.88 (m, 3H), 0.76 (d, J = 6.7 Hz, 1263, 3H). 1242, 1149, 1050, 800 cm.sup.-1 330 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 12.13 (d, film) 2963, calcd for C.sub.22H.sub.27Cl.sub.2N.sub.2O.sub.5, J = 0.6 Hz, 1H), 8.44 (d, J = 8.0 Hz, 1734, 469.1292; found, 469.1293 1H), 7.99 (d, J = 5.2 Hz, 1H), 7.34 (d, J = 2.2 Hz, 1648, 1H), 7.22 (dd, J = 8.4, 2.2 Hz, 1576, 1H), 7.13 (d, J = 8.4 Hz, 1H), 6.88 (d, J = 5.2 Hz, 1527, 1H), 5.45-5.32 (m, 1H), 1478, 4.78-4.61 (m, 1H), 3.95 (s, 3H), 3.52 (s, 1451, 1H), 2.09 (dt, J = 13.7, 6.9 Hz, 1H), 1438, 1.55 (d, J = 7.2 Hz, 3H), 1.12 (d, J = 6.3 Hz, 1262, 3H), 0.93 (d, J = 6.7 Hz, 3H), 1150, 0.76 (d, J = 6.8 Hz, 3H). 1044, 799, 730 cm.sup.-1 331 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. film) 2965, calcd for C.sub.22H.sub.27F.sub.2N.sub.2O.sub.5, 12.24-11.76 (m, 1H), 8.42 (d, J = 8.0 Hz, 1H), 1734, 437.1883; found, 437.1887 8.01 (d, J = 5.2 Hz, 1H), 7.25-7.10 (m, 1648, 1H), 6.89 (d, J = 5.1 Hz, 1H), 1576, 6.74 (dddd, J = 14.1, 11.6, 7.5, 1.9 Hz, 2H), 1528, 5.50-5.41 (m, 1H), 4.78-4.62 (m, 1502, 1H), 3.95 (s, 3H), 2.84 (dd, J = 9.1, 5.1 Hz, 1480, 1H), 2.00 (dq, J = 9.0, 6.9 Hz, 1H), 1438, 1.42 (d, J = 7.2 Hz, 3H), 1.12 (d, J = 6.3 Hz, 1322, 3H), 0.99 (d, J = 6.6 Hz, 3H), 1263, 0.70 (d, J = 6.7 Hz, 3H). 1241, 1150, 1060, 964, 848, 800, 731 cm.sup.-1 332 IR (thin .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 12.14 (d, film) 2964, J = 0.7 Hz, 1H), 8.46 (d, J = 8.0 Hz, 1733, 1H), 8.01 (d, J = 5.2 Hz, 1H), 7.13 (t, J = 7.9 Hz, 1648, 1H), 6.88 (d, J = 5.3 Hz, 1H), 1576, 6.86-6.71 (m, 2H), 5.55-5.40 (m, 1527, 1H), 4.80-4.59 (m, 1H), 3.95 (s, 3H), 1438, 2.85 (dd, J = 8.9, 5.3 Hz, 1H), 2.30 (s, 1323, 3H), 2.02 (dp, J = 13.6, 6.8 Hz, 1H), 1262, 1.40 (d, J = 7.2 Hz, 3H), 1.13 (d, J = 6.2 Hz, 1132, 800, 3H), 1.01-0.89 (m, 3H), 0.72 (d, J = 6.6 Hz, 730 cm.sup.-1 3H). .sup.13C NMR (126 MHz, CDCl.sub.3) .delta. 171.60, 168.63, 161.50 (d, J = 243.0 Hz), 155.39, 148.77, 140.46, 138.17, 130.49, 124.61, 123.34 (d, J = 14.9 Hz), 115.43 (d, J = 23.9 Hz), 109.44, 72.12, 56.09, 48.06, 34.67, 31.59, 29.04, 20.91, 18.19. 333 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 12.11 (d, film) 2964, calcd for C.sub.22H.sub.27Cl.sub.2N.sub.2O.sub.5, J = 0.6 Hz, 1H), 8.43 (d, J = 7.9 Hz, 2872, 469.1292; found, 469.1282 1H), 8.02 (d, J = 5.3 Hz, 1H), 7.37 (d, J = 2.2 Hz, 1734, 1H), 7.28 (d, J = 8.5 Hz, 1H), 1649, 7.05 (dd, J = 8.5, 2.3 Hz, 1H), 6.90 (d, J = 5.1 Hz, 1576, 1H), 5.46 (qd, J = 6.3, 4.7 Hz, 1528, 1H), 4.77-4.65 (m, 1H), 3.96 (s, 3H), 1472, 3.12 (dd, J = 9.6, 4.5 Hz, 1H), 1438, 2.02-1.92 (m, 1H), 1.48 (d, J = 7.2 Hz, 3H), 1323, 1.08 (d, J = 6.3 Hz, 3H), 1.02 (d, J = 6.6 Hz,

1263, 3H), 0.68 (d, J = 6.7 Hz, 3H). 1241, .sup.13C NMR (126 MHz, CDCl.sub.3) .delta. 171.40, 1129, 800 cm.sup.-1 168.71, 155.48, 148.85, 140.54, 136.78, 136.31, 132.55, 130.48, 130.37, 128.95, 127.06, 109.56, 72.00, 56.13, 51.39, 48.06, 34.53, 30.14, 20.75, 20.47, 18.22. 334 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 12.14 (s, film) 3368, calcd for C.sub.23H.sub.29N.sub.2O.sub.7, 1H), 8.48 (d, J = 7.9 Hz, 1H), 7.99 (d, J = 5.2 Hz, 2961, 445.1969; found, 445.1961 1H), 6.87 (d, J = 5.2 Hz, 1H), 1731, 6.69 (d, J = 8.0 Hz, 1H), 6.59 (d, J = 1.7 Hz, 1648, 1H), 6.53 (dd, J = 8.0, 1.7 Hz, 1H), 1528, 5.92 (q, J = 1.6 Hz, 2H), 5.34 (dq, J = 8.5, 1482, 6.3 Hz, 1H), 4.75-4.60 (m, 1H), 1438, 3.94 (s, 3H), 2.63 (dd, J = 8.5, 6.6 Hz, 1240, 1H), 2.03 (dq, J = 13.5, 6.8 Hz, 1H), 1037, 729 cm.sup.-1 1.54 (d, J = 7.2 Hz, 3H), 1.11 (d, J = 6.3 Hz, 3H), 0.85 (d, J = 6.7 Hz, 3H), 0.76 (d, J = 6.7 Hz, 3H). 335 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 12.13 (d, film) 3370, calcd for C.sub.23H.sub.28F.sub.3N.sub.2O.sub.6, J = 0.6 Hz, 1H), 8.44 (d, J = 7.9 Hz, 2964, 485.1894; found, 485.1896 1H), 7.99 (d, J = 5.2 Hz, 1H), 1735, 7.15-7.05 (m, 4H), 6.88 (d, J = 5.2 Hz, 1H), 1649, 5.41 (dq, J = 8.2, 6.3 Hz, 1H), 1528, 4.76-4.59 (m, 1H), 3.95 (s, 3H), 2.73 (dd, J = 8.2, 1258, 7.0 Hz, 1H), 2.09 (h, J = 6.8 Hz, 1217, 1153 cm.sup.-1 1H), 1.54 (d, J = 7.2 Hz, 3H), 1.10 (d, J = 6.4 Hz, 3H), 0.88 (d, J = 6.7 Hz, 3H), 0.74 (d, J = 6.7 Hz, 3H). .sup.19F NMR (471 MHz, CDCl.sub.3) .delta. -57.8. 336 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 12.16 (s, film) 3369, calcd for C.sub.25H.sub.35N.sub.2O.sub.6, 1H), 8.50 (d, J = 7.8 Hz, 1H), 8.00 (d, J = 5.2 Hz, 2974, 459.2490; found, 459.2468 1H), 7.08-6.94 (m, 2H), 1732, 6.87 (d, J = 5.2 Hz, 1H), 6.84-6.75 (m, 2H), 1649, 5.38 (dq, J = 8.7, 6.3 Hz, 1H), 1527, 4.79-4.58 (m, 1H), 4.50 (hept, J = 6.1 Hz, 1509, 1H), 3.95 (s, 3H), 2.65 (dd, J = 8.7, 6.3 Hz, 1239, 953, 1H), 2.15-1.97 (m, 1H), 1.55 (d, J = 7.2 Hz, 730 cm.sup.-1 3H), 1.33 (d, J = 6.0 Hz, 6H), 1.10 (d, J = 6.3 Hz, 3H), 0.84 (d, J = 6.7 Hz, 3H), 0.75 (d, J = 6.7 Hz, 3H). 337 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 12.19 (s, film) 3369, calcd for C.sub.25H.sub.35N.sub.2O.sub.6, 1H), 8.54 (d, J = 7.9 Hz, 1H), 7.99 (d, J = 5.2 Hz, 2972, 459.2490; found, 459.2476 1H), 7.14 (ddd, J = 8.5, 7.5, 1733, 1.7 Hz, 1H), 7.06 (dd, J = 7.6, 1.8 Hz, 1649, 1H), 6.93-6.74 (m, 3H), 5.47 (s, 1H), 1527, 4.84-4.62 (m, 1H), 4.54 (hept, J = 6.0 Hz, 1450, 1H), 3.94 (s, 3H), 3.45 (s, 1H), 1238, 953, 2.12 (hept, J = 6.8 Hz, 1H), 1.57 (d, J = 7.2 Hz, 752, 732 cm.sup.-1 3H), 1.33 (d, J = 6.0 Hz, 3H), 1.31 (d, J = 6.0 Hz, 3H), 1.08 (d, J = 6.2 Hz, 3H), 0.83 (d, J = 6.8 Hz, 3H), 0.76 (d, J = 6.8 Hz, 3H). 338 IR (thin HRMS-ESI (m/z) [M + Na].sup.+ .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 12.16 (s, film) 3368, calcd for C.sub.23H.sub.30N.sub.2O.sub.6Na, 1H), 8.49 (d, J = 7.9 Hz, 1H), 8.00 (d, J = 5.2 Hz, 2960, 453.1996; found, 453.1983 1H), 7.00 (d, J = 8.6 Hz, 2H), 1732, 6.88 (d, J = 5.2 Hz, 1H), 6.84-6.75 (m, 1649, 2H), 5.39 (dq, J = 8.6, 6.3 Hz, 1H), 1512, 4.76-4.63 (m, 1H), 3.95 (s, 3H), 3.79 (s, 1453, 3H), 2.66 (dd, J = 8.7, 6.4 Hz, 1H), 1241, 800, 2.07 (h, J = 6.8 Hz, 1H), 1.55 (d, J = 7.2 Hz, 730 cm.sup.-1 3H), 1.10 (d, J = 6.2 Hz, 3H), 0.85 (d, J = 6.8 Hz, 3H), 0.75 (d, J = 6.7 Hz, 3H). 339 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 12.15 (s, film) 2963, calcd for C.sub.24H.sub.33N.sub.2O.sub.5, 1H), 8.50 (d, J = 7.8 Hz, 1H), 8.00 (d, J = 5.2 Hz, 1734, 429.2310; found, 429.2381 1H), 7.21-7.02 (m, 4H), 1650, 6.88 (d, J = 5.2 Hz, 1H), 5.43 (ddq, J = 12.3, 1528, 9.6, 6.2 Hz, 1H), 4.77-4.59 (m, 1H), 1452, 1264 cm.sup.-1 3.95 (s, 3H), 3.31-3.11 (m, 1H), 2.33 (d, J = 4.9 Hz, 3H), 2.00-1.79 (m, 1H), 1.55 (d, J = 6.6 Hz, 2H), 1.41 (ddd, J = 12.2, 7.3, 4.5 Hz, 1H), 1.34-1.19 (m, 1H), 1.12-0.67 (m, 10H). 340 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 12.15 (s, film) 3370, calcd for C.sub.25H.sub.35N.sub.2O.sub.5, 1H), 8.47 (d, J = 8.1 Hz, 1H), 7.99 (d, J = 5.2 Hz, 2961, 443.2465; found, 443.2536 1H), 7.19-7.04 (m, 4H), 1528, 6.88 (d, J = 5.2 Hz, 1H), 5.46 (dq, J = 8.5, 1263, 1057 cm.sup.-1 6.2 Hz, 1H), 4.70 (p, J = 7.5 Hz, 1H), 3.95 (s, 3H), 3.32 (t, J = 7.6 Hz, 1H), 2.31 (s, 3H), 1.75-1.59 (m, 1H), 1.54 (d, J = 7.2 Hz, 3H), 1.49-1.17 (m, 3H), 1.14-0.97 (m, 4H), 0.90 (t, J = 7.4 Hz, 3H), 0.77 (t, J = 7.3 Hz, 3H). 341 ESIMS m/z 455 ([M + H].sup.+) .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 12.14 (s, 1H), 8.47 (d, J = 8.0 Hz, 1H), 7.99 (d, J = 5.2 Hz, 1H), 6.88 (d, J = 5.2 Hz, 1H), 6.62 (s, 2H), 5.58 (ddt, J = 8.0, 6.4, 1.9 Hz, 1H), 4.68 (dq, J = 9.3, 7.3 Hz, 1H), 3.95 (s, 3H), 3.19 (t, J = 7.7 Hz, 1H), 2.35-2.19 (m, 1H), 1.54 (d, J = 7.2 Hz, 3H), 1.15 (dt, J = 6.4, 1.3 Hz, 3H), 0.96 (d, J = 6.7 Hz, 3H), 0.78 (dt, J = 6.8, 1.3 Hz, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -105.84 (d, J = 1667.9 Hz), -110.02. 342 .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 12.13 (s, 1H), 8.44 (d, J = 8.0 Hz, 1H), 7.99 (d, J = 5.2 Hz, 1H), 7.08 (dd, J = 3.8, 2.0 Hz, 2H), 7.04-6.96 (m, 1H), 6.86 (dd, J = 19.5, 5.2 Hz, 1H), 5.44 (ddd, J = 7.7, 6.4, 1.3 Hz, 1H), 4.80-4.49 (m, 1H), 3.95 (s, 3H), 3.14 (t, J = 7.8 Hz, 1H), 2.09 (q, J = 6.9 Hz, 1H), 1.54 (d, J = 7.2 Hz, 3H), 1.12 (d, J = 6.3 Hz, 3H), 0.93 (d, J = 6.6 Hz, 3H), 0.75 (d, J = 6.7 Hz, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -112.37. 343 .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 12.15 (s, 1H), 8.50 (d, J = 8.0 Hz, 1H), 7.99 (d, J = 5.2 Hz, 1H), 7.24-7.07 (m, 3H), 6.96 (dddd, J = 9.5, 8.1, 2.8, 1.5 Hz, 1H), 6.87 (d, J = 5.2 Hz, 1H), 5.82-5.37 (m, 1H), 4.71 (dd, J = 7.9, 7.1 Hz, 1H), 3.62-3.24 (m, 1H), 2.31-2.21 (m, 1H), 1.57 (d, J = 7.2 Hz, 3H), 1.36 (s, 1H), 1.18-0.96 (m, 7H), 0.78 (ddd, J = 6.8, 2.7, 0.9 Hz, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 171.59, 168.70, 155.38, 148.78, 140.43, 137.03 (d, J = 9.3 Hz), 129.07-127.37 (m), 125.68 (d, J = 3.5 Hz), 114.81 (dd, J = 24.5, 2.1 Hz), 109.43, 73.22 (d, J = 5.4 Hz), 72.04 (d, J = 5.2 Hz), 56.06, 52.18-50.01 (m), 48.25, 29.65 (d, J = 3.2 Hz), 21.72 (d, J = 3.8 Hz), 20.38, 18.59 (d, J = 2.4 Hz), 18.16. .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -105.04 (d, J = 14.1 Hz). 344 ESIMS m/z 415 ([M + H].sup.+) .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 12.16 (s, 1H), 8.51 (d, J = 7.9 Hz, 1H), 8.01 (dd, J = 5.2, 3.5 Hz, 1H), 7.17 (q, J = 8.2 Hz, 1H), 7.04 (t, J = 6.0 Hz, 1H), 6.89 (td, J = 5.2, 4.7, 2.6 Hz, 3H), 5.41 (ddt, J = 17.9, 8.7, 6.2 Hz, 1H), 4.69 (p, J = 7.3 Hz, 1H), 3.94 (d, J = 5.1 Hz, 2H), 2.66 (ddd, J = 12.1, 8.8, 6.4 Hz, 1H), 2.33 (d, J = 4.2 Hz, 3H), 1.70-1.48 (m, 6H), 1.09 (dd, J = 16.5, 6.2 Hz, 2H), 0.86 (dd, J = 8.0, 6.8 Hz, 3H), 0.76 (d, J = 6.8 Hz, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 171.75, 168.73, 155.40, 148.81, 140.46, 137.37, 130.65, 130.57, 127.73, 127.39, 126.82, 109.45, 108.39, 73.18, 72.02, 56.07, 48.22, 28.31, 21.49, 21.33, 18.66, 18.33, 17.89. 345 ESIMS m/z 431 ([M + H].sup.+) .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 12.13 (s, 1H), 8.46 (d, J = 8.0 Hz, 1H), 8.00 (dd, J = 8.4, 5.2 Hz, 1H), 7.09-6.65 (m, 4H), 5.59-5.25 (m, 1H), 4.85-4.56 (m, 1H), 3.94 (d, J = 5.0 Hz, 4H), 3.27-3.08 (m, 1H), 1.54 (d, J = 7.2 Hz, 3H), 1.15 (d, J = 6.3 Hz, 3H), 0.95 (d, J = 6.7 Hz, 3H), 0.78 (d, J = 6.7 Hz, 3H). 346 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.48 (t, J = 5.4 Hz, film) 3391, calcd for C.sub.24H.sub.30FN.sub.2O.sub.6, 1H), 8.34 (d, J = 5.4 Hz, 1H), 2962, 461.2082; found, 461.2077 7.08-6.97 (m, 2H), 6.86 (ddd, J = 9.5, 1770, 6.3, 2.4 Hz, 2H), 5.43 (dq, J = 8.5, 6.4 Hz, 1743, 1H), 4.16 (d, J = 5.4 Hz, 2H), 1677, 3.92 (s, 3H), 3.03 (t, J = 7.7 Hz, 1H), 2.40 (s, 1513, 3H), 2.30 (s, 3H), 2.13-2.02 (m, 1H), 1499, 1.07 (d, J = 6.3 Hz, 3H), 0.92 (d, J = 6.7 Hz, 1311, 3H), 0.76 (d, J = 6.7 Hz, 3H). 1192, .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.43. 1175, 1009, 732 cm.sup.-1 347 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.46 (d, J = 9.5 Hz, film) 3382, calcd for C.sub.27H.sub.36FN.sub.2O.sub.6, 1H), 8.32 (d, J = 5.5 Hz, 1H), 2963, 503.2552; found, 503.2554 7.03 (dd, J = 9.1, 5.7 Hz, 2H), 6.83 (td, 1771, J = 8.4, 2.9 Hz, 1H), 6.77 (dd, J = 10.0, 1730, 2.8 Hz, 1H), 5.35 (dq, J = 9.1, 6.2 Hz, 1681, 1H), 4.66 (dd, J = 9.6, 4.8 Hz, 1H), 1499, 3.92 (s, 3H), 3.07 (dd, J = 9.1, 6.1 Hz, 1H), 1311, 2.40 (s, 3H), 2.36-2.22 (m, 4H), 1191, 2.14 (td, J = 13.4, 12.6, 5.9 Hz, 1H), 1.05 (d, 1173, 907, J = 6.2 Hz, 3H), 1.02 (d, J = 6.8 Hz, 731 cm.sup.-1 3H), 0.97 (d, J = 6.9 Hz, 3H), 0.82 (d, J = 6.8 Hz, 3H), 0.76 (d, J = 6.8 Hz, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 171.03, 168.84, 162.69, 160.91 (d, J = 244.3 Hz), 159.51, 146.61, 141.66, 139.97 (d, J = 7.3 Hz), 137.57, 133.48 (d, J = 3.2 Hz), 129.19 (d, J = 7.8 Hz), 116.95 (d, J = 20.4 Hz), 112.24 (d, J = 20.7 Hz), 109.74, 73.47, 57.33, 56.31, 49.32, 31.55, 29.38, 20.91, 20.89-20.83 (m), 20.77, 19.38, 18.63, 18.10, 17.51. .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.47. 348 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.45 (d, J = 9.5 Hz, film) 3383, calcd for C.sub.28H.sub.37FN.sub.2O.sub.6, 1H), 8.31 (d, J = 5.4 Hz, 1H), 2963, 517.2708; found, 517.2715 7.03 (dd, J = 9.5, 5.6 Hz, 2H), 6.83 (td, 1771, J = 8.4, 2.9 Hz, 1H), 6.77 (dd, J = 9.9, 1730, 2.8 Hz, 1H), 5.35 (dq, J = 9.2, 6.2 Hz, 1680, 1H), 4.71 (dd, J = 9.5, 4.9 Hz, 1H), 1499, 3.92 (s, 3H), 3.08 (dd, J = 9.2, 6.0 Hz, 1H), 1191, 2.40 (s, 3H), 2.26 (s, 3H), 2.14 (td, J = 13.3, 1173, 731 cm.sup.-1 12.8, 6.1 Hz, 1H), 2.09-1.98 (m, 1H), 1.51 (dtd, J = 16.7, 7.4, 3.6 Hz, 1H), 1.30-1.18 (m, 1H), 1.04 (d, J = 6.2 Hz, 3H), 1.00 (d, J = 6.8 Hz, 3H), 0.93 (t, J = 7.4 Hz, 3H), 0.82 (d, J = 6.8 Hz, 3H), 0.76 (d, J = 6.9 Hz, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 170.99, 168.84, 162.59, 160.91 (d, J = 244.3 Hz), 159.51, 146.60, 141.67, 139.98 (d, J = 7.5 Hz), 137.58, 133.44 (d, J = 3.3 Hz), 129.21 (d, J = 7.6 Hz), 116.95 (d, J = 20.5 Hz), 112.23 (d, J = 20.8 Hz), 109.72, 73.43, 56.98, 56.31, 49.32, 38.12, 29.31, 24.73, 20.92, 20.90-20.83 (m), 20.78, 18.48, 18.16, 15.72, 11.56. .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.47. 349 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.31 (t, J = 5.8 Hz, film) 3378, calcd for C.sub.28H.sub.38FN.sub.2O.sub.6, 2H), 7.08-6.96 (m, 2H), 2959, 517.2708; found, 517.2707 6.84 (td, J = 8.4, 2.9 Hz, 1H), 6.78 (dd, J = 9.9, 1772, 2.8 Hz, 1H), 5.33 (dq, J = 8.9, 6.3 Hz, 1733, 1H), 4.72 (dt, J = 9.0, 7.0 Hz, 1H), 1679, 3.91 (s, 3H), 3.06 (dd, J = 8.9, 6.5 Hz, 1499, 1H), 2.39 (s, 3H), 2.26 (s, 3H), 1191, 2.15-2.04 (m, 1H), 1.78-1.59 (m, 3H), 1173, 1.05 (d, J = 6.2 Hz, 3H), 0.99-0.93 (m, 6H), 1049, 825 cm.sup.-1 0.84 (d, J = 6.8 Hz, 3H), 0.75 (d, J = 6.8 Hz,

3H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 172.05, 168.83, 162.46, 160.90 (d, J = 244.3 Hz), 159.52, 146.57, 141.63, 139.94 (d, J = 7.5 Hz), 137.58, 133.69 (d, J = 3.3 Hz), 129.18 (d, J = 6.9 Hz), 116.90 (d, J = 20.5 Hz), 112.25 (d, J = 20.6 Hz), 109.74, 73.52, 56.30, 51.04, 49.33, 41.69, 29.59, 24.93, 23.03, 21.98, 20.94, 20.92-20.86 (m), 20.76, 18.94, 17.82. .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.54. 350 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.46 (t, J = 5.4 Hz, film) 3387, calcd for C.sub.26H.sub.34FN.sub.2O.sub.7, 1H), 8.33 (d, J = 5.4 Hz, 1H), 2961, 505.2345; found, 505.2339 7.08-6.99 (m, 2H), 6.90-6.80 (m, 1767, 2H), 5.43 (dq, J = 8.2, 6.3 Hz, 1H), 1742, 4.15 (d, J = 5.4 Hz, 2H), 3.91 (s, 3H), 3.82 (t, 1678, J = 6.6 Hz, 2H), 3.41 (s, 3H), 1498, 3.09-2.95 (m, 3H), 2.30 (s, 3H), 2.07 (h, J = 6.8 Hz, 1208, 1H), 1.07 (d, J = 6.3 Hz, 3H), 1112, 0.92 (d, J = 6.7 Hz, 3H), 0.76 (d, J = 6.8 Hz, 1047, 3H). 1009, 730 cm.sup.-1 .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.43. 351 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.44 (d, J = 9.5 Hz, film) 3383, calcd for C.sub.29H.sub.40FN.sub.2O.sub.7, 1H), 8.32 (d, J = 5.4 Hz, 1H), 2963, 547.2814; found, 547.2813 7.09-6.98 (m, 2H), 6.83 (td, J = 8.4, 1769, 2.9 Hz, 1H), 6.77 (dd, J = 10.0, 2.8 Hz, 1730, 1H), 5.35 (dq, J = 9.1, 6.2 Hz, 1H), 1681, 4.65 (dd, J = 9.5, 4.8 Hz, 1H), 3.91 (s, 3H), 1499, 3.81 (t, J = 6.6 Hz, 2H), 3.40 (s, 3H), 1311, 3.07 (dd, J = 9.1, 6.1 Hz, 1H), 2.99 (t, J = 6.7 Hz, 1110, 826 cm.sup.-1 2H), 2.34-2.21 (m, 4H), 2.14 (dq, J = 13.4, 6.5 Hz, 1H), 1.05 (d, J = 6.2 Hz, 3H), 1.01 (d, J = 6.8 Hz, 3H), 0.97 (d, J = 6.9 Hz, 3H), 0.82 (d, J = 6.8 Hz, 3H), 0.76 (d, J = 6.9 Hz, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.47. 352 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.43 (d, J = 9.4 Hz, film) 3382, calcd for C.sub.30H.sub.42FN.sub.2O.sub.7, 1H), 8.31 (d, J = 5.4 Hz, 1H), 2963, 561.2971; found, 561.2969 7.06-6.96 (m, 2H), 6.83 (td, J = 8.4, 1769, 2.9 Hz, 1H), 6.77 (dd, J = 10.0, 2.8 Hz, 1730, 1H), 5.35 (dq, J = 9.1, 6.2 Hz, 1H), 1681, 4.69 (dd, J = 9.5, 4.9 Hz, 1H), 3.91 (s, 3H), 1499, 3.81 (t, J = 6.6 Hz, 2H), 3.41 (s, 3H), 1111, 3.07 (dd, J = 9.2, 6.0 Hz, 1H), 2.99 (t, J = 6.7 Hz, 1046, 825, 2H), 2.26 (s, 3H), 731 cm.sup.-1 2.18-2.08 (m, 1H), 2.08-1.97 (m, 1H), 1.50 (dddd, J = 13.3, 11.3, 6.8, 3.8 Hz, 1H), 1.29-1.17 (m, 1H), 1.04 (d, J = 6.2 Hz, 3H), 0.99 (d, J = 6.9 Hz, 3H), 0.93 (t, J = 7.4 Hz, 3H), 0.82 (d, J = 6.8 Hz, 3H), 0.76 (d, J = 6.8 Hz, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 170.99, 169.35, 162.55, 160.91 (d, J = 243.9 Hz), 159.52, 146.64, 141.69, 139.97 (d, J = 7.5 Hz), 137.44, 133.44 (d, J = 3.1 Hz), 129.20 (d, J = 8.2 Hz), 116.95 (d, J = 20.3 Hz), 112.24 (d, J = 20.7 Hz), 109.72, 73.43, 67.65, 58.75, 56.97, 56.34, 49.30, 38.13, 34.69, 29.32, 24.73, 20.92, 20.90-20.86 (m), 18.49, 18.15, 15.72, 11.55. .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.46. 353 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.31 (t, J = 3.9 Hz, film) 3377, calcd for C.sub.30H.sub.42FN.sub.2O.sub.7, 2H), 7.08-6.98 (m, 2H), 2958, 561.2971; found, 561.2974 6.84 (td, J = 8.4, 2.9 Hz, 1H), 6.78 (dd, J = 10.0, 1769, 2.8 Hz, 1H), 5.37-5.27 (m, 1H), 1733, 4.79-4.63 (m, 1H), 3.91 (s, 3H), 1679, 3.81 (t, J = 6.7 Hz, 2H), 3.40 (s, 3H), 1499, 3.06 (dd, J = 8.9, 6.5 Hz, 1H), 2.98 (t, J = 6.7 Hz, 1309, 2H), 2.26 (s, 3H), 2.09 (h, J = 6.8 Hz, 1110, 1H), 1.75-1.62 (m, 3H), 1.05 (d, J = 6.2 Hz, 1049, 826 cm.sup.-1 3H), 0.99-0.93 (m, 6H), 0.84 (d, J = 6.8 Hz, 3H), 0.74 (d, J = 6.8 Hz, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 172.06, 169.33, 162.42, 160.91 (d, J = 244.3 Hz), 159.53, 146.61, 141.64, 139.93 (d, J = 7.6 Hz), 137.45, 133.69 (d, J = 3.1 Hz), 129.19 (d, J = 8.0 Hz), 116.91 (d, J = 20.5 Hz), 112.25 (d, J = 20.6 Hz), 109.74, 73.51, 67.65, 58.74, 56.33, 51.03, 49.32, 41.74, 34.69, 29.60, 24.91, 23.05, 21.97, 21.01-20.80 (m), 20.94, 18.95, 17.82. .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.54. 354 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.45 (d, J = 8.1 Hz, film) 3383, calcd for C.sub.29H.sub.38FN.sub.2O.sub.6, 1H), 8.31 (d, J = 5.4 Hz, 1H), 2960, 529.2708; found, 529.2705 7.05 (dd, J = 8.6, 5.9 Hz, 1H), 6.99 (d, J = 5.5 Hz, 1736, 1H), 6.90-6.77 (m, 2H), 1499, 5.35 (dq, J = 8.9, 6.2 Hz, 1H), 1208, 4.77-4.64 (m, 1H), 3.89 (s, 3H), 3.15 (q, J = 8.0 Hz, 1122, 730 cm.sup.-1 1H), 3.11-3.03 (m, 1H), 2.29 (s, 3H), 2.21-1.97 (m, 6H), 1.83-1.70 (m, 2H), 1.70-1.57 (m, 1H), 1.49 (d, J = 7.2 Hz, 3H), 1.06 (d, J = 6.2 Hz, 3H), 0.86 (d, J = 6.8 Hz, 3H), 0.77 (d, J = 6.8 Hz, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.44. 355 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.42 (d, J = 10.8 Hz, film) 3382, calcd for C.sub.28H.sub.38FN.sub.2O.sub.6, 1H), 8.32 (d, J = 5.4 Hz, 2968, 517.2708; found, 517.2702 1H), 7.05 (dd, J = 8.6, 5.9 Hz, 1H), 1734, 6.99 (d, J = 5.5 Hz, 1H), 6.91-6.77 (m, 2H), 1679, 5.35 (dq, J = 8.7, 6.2 Hz, 1H), 1499, 4.77-4.66 (m, 1H), 3.89 (s, 3H), 3.07 (dd, J = 8.8, 1155, 6.5 Hz, 1H), 2.77 (q, J = 6.9 Hz, 1109, 1H), 2.29 (s, 3H), 2.11 (h, J = 6.7 Hz, 1059, 731 cm.sup.-1 1H), 1.92 (dp, J = 14.2, 7.0 Hz, 1H), 1.65 (dt, J = 13.9, 7.2 Hz, 1H), 1.49 (d, J = 7.2 Hz, 3H), 1.37-1.30 (m, 3H), 1.05 (dd, J = 7.8, 7.0 Hz, 6H), 0.86 (d, J = 6.8 Hz, 3H), 0.77 (d, J = 6.8 Hz, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.44. 356 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.47 (d, J = 8.1 Hz, film) 3380, calcd for C.sub.28H.sub.38FN.sub.2O.sub.6, 1H), 8.32 (d, J = 5.4 Hz, 1H), 2960, 517.2708; found, 517.2706 7.05 (dd, J = 8.6, 5.9 Hz, 1H), 7.00 (d, J = 5.4 Hz, 1678, 1H), 6.88-6.77 (m, 2H), 1499, 5.36 (dq, J = 8.9, 6.3 Hz, 1H), 4.70 (dq, J = 8.2, 1311, 7.2 Hz, 1H), 3.90 (s, 3H), 3.08 (dd, 1149, J = 8.9, 6.5 Hz, 1H), 2.58 (d, J = 7.1 Hz, 1049, 731 cm.sup.-1 2H), 2.35-2.20 (m, 4H), 2.17-2.05 (m, 1H), 1.49 (d, J = 7.2 Hz, 3H), 1.09-1.03 (m, 9H), 0.86 (d, J = 6.7 Hz, 3H), 0.77 (d, J = 6.8 Hz, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.43. 357 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.50 (d, J = 8.0 Hz, film) 3379, calcd for C.sub.26H.sub.34FN.sub.2O.sub.6, 1H), 8.32 (d, J = 5.5 Hz, 1H), 2961, 489.2395; found, 489.2389 7.05 (dd, J = 8.6, 5.9 Hz, 1H), 7.01 (d, J = 5.4 Hz, 1734, 1H), 6.89-6.78 (m, 2H), 1676, 5.36 (dq, J = 8.9, 6.2 Hz, 1H), 1499, 4.76-4.64 (m, 1H), 3.91 (s, 3H), 3.08 (dd, J = 8.9, 1310, 6.5 Hz, 1H), 2.73 (q, J = 7.5 Hz, 2H), 1211, 2.29 (s, 3H), 2.11 (h, J = 6.8 Hz, 1H), 1125, 1.50 (d, J = 7.2 Hz, 3H), 1.28 (t, J = 7.5 Hz, 1049, 731 cm.sup.-1 3H), 1.06 (d, J = 6.3 Hz, 3H), 0.86 (d, J = 6.8 Hz, 3H), 0.77 (d, J = 6.8 Hz, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -117.43. 358 IR (thin ESIMS m/z 471.2 .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 8.56 (s, film) 3378, ([M + H].sup.+) 1H), 8.34 (d, J = 5.5 Hz, 1H), 2959, 7.04-6.98 (m, 2H), 6.95-6.84 (m, 2H), 1770, 5.37 (dq, J = 9.4, 6.2 Hz, 1H), 1731, 4.76-4.65 (m, 1H), 3.91 (s, 3H), 3.10 (dd, J = 9.1, 1675, 5.9 Hz, 1H), 2.40 (s, 3H), 2.29 (s, 3H), 1504, 2.27 (s, 3H), 2.14 (dp, J = 14.1, 7.4, 6.9 Hz, 1451, 1H), 1.52 (d, J = 7.1 Hz, 3H), 1435, 1.05 (d, J = 6.2 Hz, 3H), 0.84 (d, J = 6.8 Hz, 1365, 3H), 0.80 (d, J = 6.8 Hz, 3H). 1309, 1199, 1174, 1044, 907, 804, 729 cm.sup.-1 359 IR (thin ESIMS m/z 475.2 .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 8.53 (s, film) 3381, ([M + H].sup.+) 1H), 8.34 (d, J = 5.5 Hz, 1H), 7.11 (td, J = 8.0, 2961, 5.9 Hz, 1H), 7.01 (d, J = 5.5 Hz, 1770, 1H), 6.90 (dt, J = 8.8, 4.9 Hz, 2H), 1732, 5.38 (dq, J = 8.9, 6.2 Hz, 1H), 1675, 4.75-4.63 (m, 1H), 3.91 (s, 3H), 3.14 (t, J = 7.7 Hz, 1506, 1H), 2.40 (s, 3H), 2.22 (d, J = 2.4 Hz, 1457, 3H), 2.14 (dq, J = 13.5, 6.9 Hz, 1H), 1436, 1.51 (d, J = 7.1 Hz, 3H), 1.06 (d, J = 6.3 Hz, 1366, 3H), 0.86 (d, J = 6.8 Hz, 3H), 1310, 0.78 (d, J = 6.9 Hz, 3H). 1199, 1164, 1041, 907, 785, 731 cm.sup.-1 360 IR (thin ESIMS m/z 461.2 .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 8.55 (s, film) 3381, ([M + H].sup.+) 1H), 8.34 (d, J = 5.4 Hz, 1H), 2963, 7.22-7.17 (m, 1H), 7.14 (td, J = 7.5, 1.9 Hz, 1771, 1H), 7.08 (td, J = 7.5, 1.2 Hz, 1H), 1734, 7.00 (d, J = 5.4 Hz, 2H), 5.52-5.37 (m, 1H), 1676, 4.75-4.60 (m, 1H), 3.91 (s, 3H), 1508, 3.19 (t, J = 7.7 Hz, 1H), 2.40 (s, 3H), 1490, 2.18-2.09 (m, 1H), 1.50 (d, J = 7.2 Hz, 3H), 1453, 1.11 (d, J = 6.3 Hz, 3H), 0.91 (d, J = 6.7 Hz, 1436, 3H), 0.77 (d, J = 6.7 Hz, 3H). 1366, 1310, 1202, 1175, 1050, 907, 759, 732 cm.sup.-1 361 IR (thin ESIMS m/z 475.2 .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 8.53 (s, film) 3377, ([M + H].sup.+) 1H), 8.33 (d, J = 5.4 Hz, 1H), 7.07 (dd, 2961, J = 8.2, 6.2 Hz, 1H), 7.01 (d, J = 5.4 Hz, 1770, 1H), 6.88-6.73 (m, 2H), 1734, 5.41-5.24 (m, 1H), 4.76-4.64 (m, 1H), 3.91 (s, 1676, 3H), 3.10 (t, J = 7.8 Hz, 1H), 2.40 (s, 1500, 3H), 2.27 (s, 3H), 2.16-2.08 (m, 1H), 1453, 1.50 (d, J = 7.2 Hz, 3H), 1.08 (d, J = 6.3 Hz, 1436, 3H), 0.88 (d, J = 6.8 Hz, 3H), 1365, 0.80 (d, J = 6.8 Hz, 3H). 1310, 1201, 1175, 1048, 907, 805, 731 cm.sup.-1 362 IR (thin ESIMS m/z 471.2 .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.56 (s, film) 3376, ([M + H].sup.+) 1H), 8.34 (d, J = 5.5 Hz, 1H), 7.01 (d, J = 5.5 Hz, 2959, 1H), 6.96 (d, J = 2.9 Hz, 3H), 1771, 5.46-5.29 (m, 1H), 4.77-4.65 (m, 1731, 1H), 3.91 (s, 3H), 3.09 (dd, J = 9.2, 5.9 Hz, 1676, 1H), 2.36 (s, 3H), 2.28 (s, 6H), 1505, 2.19-2.07 (m, 1H), 1.51 (d, J = 7.1 Hz, 3H), 1452, 1.04 (d, J = 6.2 Hz, 3H), 0.84 (d, J = 6.8 Hz, 1437, 3H), 0.79 (d, J = 6.8 Hz, 3H). 1200, 1175, 1045, 823 cm.sup.-1 363 IR (thin ESIMS m/z 471.2 .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.57 (s, film) 3377, ([M + H].sup.+) 1H), 8.34 (d, J = 5.4 Hz, 1H), 2961, 7.06-6.99 (m, 3H), 6.97-6.92 (m, 1H), 1771, 5.39 (dq, J = 12.5, 6.5 Hz, 1H), 4.69 (dt, J = 8.1, 1733, 7.1 Hz, 1H), 3.91 (s, 3H), 3.25 (dd, 1677, J = 9.2, 6.0 Hz, 1H), 2.36 (s, 3H), 1507, 2.28 (s, 3H), 2.23 (s, 3H), 2.13 (dt, J = 14.1, 1452, 7.1 Hz, 1H), 1.52 (d, J = 7.2 Hz, 3H), 1437, 1.04 (d, J = 6.2 Hz, 3H), 0.84 (d, J = 6.7 Hz, 1365, 3H), 0.79 (d, J = 6.9 Hz, 3H). 1310, 1202,

1175, 1043 cm.sup.-1 364 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 8.55 (s, film) 3382, calcd for C.sub.25H.sub.33N.sub.2O.sub.6, 1H), 8.34 (d, J = 5.5 Hz, 1H), 2960, 457.2333; found, 457.2332 7.18-7.06 (m, 4H), 7.01 (d, J = 5.4 Hz, 1H), 1771, 5.39 (dq, J = 9.3, 6.2 Hz, 1H), 1732, 4.75-4.66 (m, 1H), 3.91 (s, 3H), 3.14 (dd, J = 9.3, 1676, 6.2 Hz, 1H), 2.40 (s, 3H), 2.32 (s, 1507, 3H), 2.21-2.10 (m, 1H), 1.51 (d, J = 7.1 Hz, 1200, 3H), 1.05 (d, J = 6.2 Hz, 3H), 1175, 731 cm.sup.-1 0.86 (d, J = 6.9 Hz, 3H), 0.80 (d, J = 6.9 Hz, 3H). 365 IR (thin ESIMS m/z 479.2 .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 8.52 (s, film) 2964, ([M + H].sup.+) 1H), 8.33 (d, J = 5.4 Hz, 1H), 7.10 (td, J = 8.4, 1770, 6.4 Hz, 1H), 7.01 (d, J = 5.5 Hz, 1734, 1H), 6.85-6.79 (m, 1H), 6.75 (ddd, J = 10.2, 1675, 8.9, 2.6 Hz, 1H), 5.41 (tt, J = 7.1, 1502, 5.8 Hz, 1H), 4.83-4.58 (m, 1H), 1453, 3.91 (s, 3H), 3.13 (t, J = 7.7 Hz, 1H), 2.40 (s, 1309, 3H), 2.09 (td, J = 13.3, 6.5 Hz, 1H), 1192, 1.49 (d, J = 7.2 Hz, 3H), 1.10 (d, J = 6.3 Hz, 1174, 3H), 0.92 (d, J = 6.8 Hz, 3H), 1049, 965, 0.75 (d, J = 6.7 Hz, 3H). 907, 846, 730 cm.sup.-1 366 IR (thin ESIMS m/z 475.2 .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 8.55 (s, film) 2962, ([M + H].sup.+) 1H), 8.34 (d, J = 5.5 Hz, 1H), 1770, 7.05-6.95 (m, 2H), 6.89 (dd, J = 7.6, 1.5 Hz, 1733, 1H), 6.85-6.77 (m, 1H), 1676, 5.50-5.38 (m, 1H), 4.83-4.55 (m, 1H), 3.91 (s, 1506, 3H), 3.13 (t, J = 7.7 Hz, 1H), 2.40 (s, 1452, 3H), 2.32 (s, 3H), 2.10 (dt, J = 13.5, 6.8 Hz, 1310, 1H), 1.50 (d, J = 7.1 Hz, 3H), 1197, 1.10 (d, J = 6.3 Hz, 3H), 0.90 (d, J = 6.7 Hz, 1174, 3H), 0.76 (d, J = 6.7 Hz, 3H). 1049, 907, .sup.13C NMR (126 MHz, CDCl.sub.3) .delta. 172.25, 823, 731 cm.sup.-1 168.92, 162.36, 160.50, 159.45, 146.65, 141.61, 138.33 (d, J = 8.2 Hz), 137.50, 130.10, 124.31 (d, J = 3.0 Hz), 122.50 (d, J = 15.0 Hz), 115.94 (d, J = 23.8 Hz), 109.70, 72.47, 56.28, 48.17, 28.32, 21.07, 20.90, 20.77, 18.96, 18.52, 17.42. 367 IR (thin ESIMS m/z 511.1 ([M].sup.+) .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 8.51 (s, film) 2963, 1H), 8.33 (d, J = 5.4 Hz, 1H), 7.36 (d, J = 2.2 Hz, 1771, 1H), 7.22 (dd, J = 8.5, 2.2 Hz, 1735, 1H), 7.13 (d, J = 8.4 Hz, 1H), 7.01 (d, J = 5.4 Hz, 1677, 1H), 5.37 (t, J = 7.3 Hz, 1H), 1508, 4.83-4.56 (m, 1H), 3.91 (s, 3H), 1365, 3.51 (s, 1H), 2.40 (s, 3H), 2.16-1.99 (m, 1310, 1H), 1.50 (d, J = 7.2 Hz, 3H), 1.10 (d, J = 6.3 Hz, 1200, 3H), 0.92 (d, J = 6.7 Hz, 3H), 1175, 0.76 (d, J = 6.8 Hz, 3H). 1044, 825, 732 cm.sup.-1 368 IR (thin ESIMS m/z 479.2 .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 8.49 (s, film) 3379, ([M + H].sup.+) 1H), 8.34 (d, J = 5.4 Hz, 1H), 7.26 (s, 2967, 1H), 7.02 (dd, J = 5.5, 2.3 Hz, 1H), 1770, 6.82-6.71 (m, 2H), 5.45 (td, J = 6.2, 4.7 Hz, 1733, 1H), 4.75-4.59 (m, 1H), 3.92 (d, J = 2.5 Hz, 1675, 3H), 2.82 (dd, J = 9.3, 4.8 Hz, 1502, 1H), 2.39 (s, 3H), 2.01 (ddt, J = 15.8, 1192, 13.3, 6.8 Hz, 1H), 1.39 (d, J = 7.1 Hz, 1173, 965, 3H), 1.08 (d, J = 6.3 Hz, 3H), 0.99 (d, J = 6.6 Hz, 846, 731 cm.sup.-1 3H), 0.70 (d, J = 6.6 Hz, 3H). 369 IR (thin ESIMS m/z 475.2 .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 8.62 (dt, film) 2965, ([M + H].sup.+) J = 4.3, 1.8 Hz, 1H), 8.35 (d, J = 5.5 Hz, 1771, 1H), 7.70 (tt, J = 7.7, 1.8 Hz, 1H), 1732, 7.31 (dd, J = 7.7, 5.8 Hz, 1H), 7.01 (d, J = 5.5 Hz, 1676, 1H), 6.82 (dd, J = 9.4, 7.0 Hz, 1506, 2H), 5.53-5.33 (m, 1H), 1437, 4.76-4.54 (m, 1H), 3.91 (s, 3H), 2.83 (dd, J = 9.2, 1310, 5.0 Hz, 1H), 2.39 (s, 3H), 2.31 (s, 3H), 1190, 1.36 (d, J = 7.1 Hz, 3H), 1.10 (d, J = 6.3 Hz, 1175, 3H), 0.98 (d, J = 6.6 Hz, 3H), 1061, 0.72 (d, J = 6.8 Hz, 3H). 1008, 821, 803 cm.sup.-1 370 IR (thin ESIMS m/z 511.1 .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 8.50 (s, film) 2964, ([M + H].sup.+) 1H), 8.35 (d, J = 5.4 Hz, 1H), 1771, 7.41-7.30 (m, 2H), 7.07 (dd, J = 8.5, 2.2 Hz, 1733, 1H), 7.03 (d, J = 5.4 Hz, 1H), 5.44 (qd, 1714, J = 6.2, 4.3 Hz, 1H), 4.80-4.61 (m, 1676, 1H), 3.92 (d, J = 1.9 Hz, 3H), 3.10 (dd, 1506, J = 9.8, 4.3 Hz, 1H), 2.40 (s, 3H), 1472, 2.04-1.88 (m, 1H), 1.44 (d, J = 7.2 Hz, 3H), 1365, 1.05 (d, J = 6.3 Hz, 3H), 1.02 (d, J = 6.6 Hz, 1310, 3H), 0.68 (d, J = 6.7 Hz, 3H). 1192, .sup.13C NMR (126 MHz, CDCl.sub.3) .delta. 171.98, 1175, 826, 168.88, 162.37, 159.57, 149.73, 146.66, 804, 734 cm.sup.-1 141.41, 137.63, 136.93, 136.28, 132.49, 130.70, 128.86, 127.08, 123.76, 109.88, 71.68, 56.33, 48.10, 30.13, 20.73, 20.64, 18.62, 18.30. 371 IR (thin ESIMS m/z 577.3 .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.33 (d, J = 5.5 Hz, film) 2961, ([M + H].sup.+) 1H), 7.04 (dd, J = 8.6, 5.9 Hz, 1773, 1H), 6.95 (d, J = 5.6 Hz, 1H), 1742, 6.91-6.79 (m, 2H), 5.44-5.31 (m, 1H), 1685, 5.25 (q, J = 7.0 Hz, 1H), 4.31 (q, J = 7.1 Hz, 1594, 2H), 3.98-3.85 (m, 5H), 3.01 (t, J = 7.6 Hz, 1490, 1H), 2.31 (s, 3H), 1441, 2.15-2.04 (m, 1H), 1.63 (d, J = 7.0 Hz, 3H), 1375, 1.36 (t, J = 7.2 Hz, 3H), 1.01 (d, J = 6.3 Hz, 1342, 3H), 0.90 (d, J = 6.8 Hz, 3H), 0.87 (t, J = 7.2 Hz, 1306, 3H), 0.77 (d, J = 6.7 Hz, 3H). 1246, 1217, 1201, 1090 cm.sup.-1 372 IR (thin ESIMS m/z 505.3 .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 8.47 (d, J = 8.1 Hz, film) 3379, ([M + H].sup.+) 1H), 8.34 (d, J = 5.5 Hz, 1H), 2962, 7.08-6.99 (m, 2H), 6.88-6.79 (m, 1767, 2H), 5.36 (dq, J = 8.9, 6.3 Hz, 1H), 1734, 4.81-4.69 (m, 1H), 4.36 (q, J = 7.1 Hz, 2H), 1678, 3.94 (s, 3H), 3.08 (dd, J = 8.9, 6.5 Hz, 1499, 1H), 2.29 (m, 3H), 2.15-2.05 (m, 1H), 1312, 1.50 (d, J = 7.1 Hz, 3H), 1.41 (t, J = 7.1 Hz, 1251, 3H), 1.06 (d, J = 6.3 Hz, 3H), 1215, 0.86 (d, J = 6.8 Hz, 3H), 0.77 (d, J = 6.8 Hz, 1051, 731 cm.sup.-1 3H). 373 IR (thin ESIMS m/z 519.3 .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.44 (d, J = 8.1 Hz, film) 3384, ([M + H].sup.+) 1H), 8.33 (d, J = 5.4 Hz, 1H), 2981, 7.08-6.97 (m, 2H), 6.91-6.75 (m, 1764, 2H), 5.44-5.31 (m, 1H), 4.98 (dq, J = 12.9, 1736, 6.4 Hz, 1H), 4.81-4.61 (m, 1H), 1681, 3.93 (s, 3H), 3.08 (dd, J = 8.9, 6.5 Hz, 1500, 1H), 2.29 (s, 3H), 2.11 (dt, J = 13.5, 6.8 Hz, 1313, 1H), 1.50 (d, J = 7.1 Hz, 3H), 1259, 1.41 (d, J = 6.3 Hz, 6H), 1.06 (d, J = 6.3 Hz, 1217, 3H), 0.86 (d, J = 6.8 Hz, 3H), 0.77 (d, J = 6.8 Hz, 1180, 3H). 1100, 915 cm.sup.-1 374 IR (thin ESIMS m/z 517.3 .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.40 (s, film) 3382, ([M + H].sup.+) 1H), 8.31 (d, J = 5.4 Hz, 1H), 7.05 (dd, 2968, J = 8.5, 5.9 Hz, 1H), 6.98 (d, J = 5.5 Hz, 2874, 1H), 6.91-6.72 (m, 2H), 5.35 (dq, J = 8.9, 1756, 6.3 Hz, 1H), 4.77-4.62 (m, 1H), 1735, 3.89 (s, 3H), 3.07 (dd, J = 8.8, 6.6 Hz, 1681, 1H), 2.29 (s, 3H), 2.11 (h, J = 6.7 Hz, 1611, 1H), 1.49 (d, J = 7.1 Hz, 3H), 1.41 (s, 1500, 9H), 1.05 (d, J = 6.3 Hz, 3H), 0.86 (d, J = 6.8 Hz, 1311, 3H), 0.77 (d, J = 6.8 Hz, 3H). 1274, .sup.13C NMR (126 MHz, CDCl.sub.3) .delta. 176.05, 1208, 172.39, 162.25, 160.89 (d, J = 244.3 Hz), 1154, 159.38, 146.49, 142.15, 139.92, 1108, 137.85, 133.67, 116.93 (d, J = 20.4 Hz), 1060, 819, 112.29 (d, J = 20.6 Hz), 109.49, 73.65, 730 cm.sup.-1 56.29, 53.43, 49.29, 48.13, 39.15, 29.67, 27.17, 20.92, 18.92, 18.66, 17.87. 375 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 8.49 (s, film) 3382, calcd for C.sub.27H.sub.37N.sub.2O.sub.6, 1H), 8.33 (d, J = 5.4 Hz, 1H), 2970, 485.2646; found, 485.2642 7.18-7.06 (m, 4H), 6.99 (d, J = 5.5 Hz, 1H), 2875, 5.39 (dq, J = 9.2, 6.2 Hz, 1H), 1762, 4.76-4.66 (m, 1H), 3.89 (s, 3H), 3.13 (dd, J = 9.2, 1733, 6.2 Hz, 1H), 2.95 (p, J = 7.0 Hz, 1678, 1H), 2.32 (s, 3H), 2.21-2.10 (m, 1H), 1504, 1.50 (d, J = 7.1 Hz, 3H), 1.36 (dd, J = 7.0, 1208, 730 cm.sup.-1 0.9 Hz, 6H), 1.05 (d, J = 6.2 Hz, 3H), 0.86 (d, J = 6.8 Hz, 3H), 0.80 (d, J = 6.8 Hz, 3H). 376 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 8.59 (s, film) calcd for C.sub.27H.sub.37N.sub.2O.sub.7, 1H), 8.33 (d, J = 5.5 Hz, 1H), 7.14 (td, J = 7.8, 3383, 2974, 501.2601; found, 501.2515 1.7 Hz, 1H), 7.06 (dd, J = 7.5, 1.7 Hz, 1771, 1H), 7.00 (d, J = 5.5 Hz, 1H), 1732, 6.94-6.73 (m, 2H), 5.45 (s, 1H), 1676, 4.86-4.64 (m, 1H), 4.54 (hept, J = 6.0 Hz, 1H), 1506, 3.90 (s, 3H), 3.44 (s, 1H), 2.40 (s, 3H), 1193, 2.14 (dq, J = 13.3, 6.4 Hz, 1H), 1.52 (d, 1174, 751 cm.sup.-1 J = 7.1 Hz, 3H), 1.33 (d, J = 6.0 Hz, 3H), 1.31 (d, J = 6.0 Hz, 3H), 1.05 (d, J = 6.1 Hz, 3H), 0.83 (d, J = 6.8 Hz, 3H), 0.76 (d, J = 6.8 Hz, 3H). 377 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 8.56 (s, film) 3381, calcd for C.sub.27H.sub.37N.sub.2O.sub.7, 1H), 8.34 (d, J = 5.4 Hz, 1H), 7.00 (d, J = 5.5 Hz, 2975, 501.2601; found, 501.2493 1H), 6.99-6.96 (m, 2H), 1771, 6.81-6.76 (m, 2H), 5.36 (dq, J = 8.6, 6.2 Hz, 1732, 1H), 4.75-4.62 (m, 1H), 1676, 4.51 (hept, J = 6.0 Hz, 1H), 3.91 (s, 3H), 1507, 2.64 (dd, J = 8.8, 6.3 Hz, 1H), 2.40 (s, 1175, 730 cm.sup.-1 3H), 2.12-2.02 (m, 1H), 1.50 (d, J = 7.1 Hz, 3H), 1.33 (d, J = 6.0 Hz, 6H), 1.08 (d, J = 6.3 Hz, 3H), 0.84 (d, J = 6.8 Hz, 3H), 0.75 (d, J = 6.7 Hz, 3H). 378 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 8.33 (d, J = 7.8 Hz, film) 3381, calcd for C.sub.26H.sub.32F.sub.3N.sub.2O.sub.8, 1H), 8.28 (d, J = 5.3 Hz, 1H), 2964, 557.2107; found, 557.2107 7.15-7.04 (m, 4H), 6.96 (d, J = 5.4 Hz, 1737, 1H), 5.75 (s, 2H), 5.40 (dq, J = 8.3, 6.3 Hz, 1677, 1H), 4.70 (p, J = 7.3 Hz, 1H), 1506, 3.92 (s, 3H), 2.73 (dd, J = 8.3, 6.9 Hz, 1H), 1256, 2.15-2.04 (m, 4H), 1.51 (d, J = 7.2 Hz, 1201, 3H), 1.09 (d, J = 6.3 Hz, 3H), 0.88 (d, J = 6.7 Hz, 1160, 1004 cm.sup.-1 3H), 0.74 (d, J = 6.8 Hz, 3H). 379 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 8.38 (d, J = 7.8 Hz, film) 3382, calcd for C.sub.28H.sub.39N.sub.2O.sub.8, 1H), 8.29 (d, J = 5.3 Hz, 1H), 2976, 531.2701; found, 531.2688 6.98 (d, J = 8.7 Hz, 2H), 6.95 (d, J = 5.4 Hz, 1755, 1H), 6.79 (d, J = 8.6 Hz, 2H), 1733, 5.80-5.71 (m, 2H), 5.37 (dq, J = 8.8, 6.3 Hz, 1675, 1H), 4.80-4.64 (m, 1H), 4.51 (hept, J = 6.1 Hz, 1506, 1H), 3.91 (s, 3H), 2.65 (dd, J = 8.8, 1236, 6.3 Hz, 1H), 2.15-2.00 (m, 4H), 1201, 955, 1.52 (d, J = 7.2 Hz, 3H), 1.33 (d, J = 6.1 Hz, 829 cm.sup.-1 6H), 1.08 (d, J = 6.3 Hz, 3H), 0.84 (d, J = 6.7 Hz, 3H), 0.75 (d, J = 6.8 Hz, 3H). 380 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 8.54 (s, film) 3380, calcd for C.sub.25H.sub.31N.sub.2O.sub.8, 1H), 8.34 (d, J = 5.5 Hz, 1H), 7.01 (d, J = 5.5 Hz, 2961, 487.2080; found, 487.2065 1H), 6.70 (d, J = 7.9 Hz, 1H), 1770, 6.60 (d, J = 1.6 Hz, 1H), 6.54 (dd, J = 8.0, 1731, 1.7 Hz, 1H), 5.93 (q, J = 1.5 Hz, 1675, 2H), 5.33 (dq, J = 8.6, 6.3 Hz, 1H), 1504, 4.75-4.63 (m, 1H), 3.91 (s, 3H), 2.63 (dd, J = 8.5, 1488, 6.6 Hz, 1H), 2.40 (s, 3H), 1192, 2.09-2.00 (m, 1H), 1.49 (d, J = 7.2 Hz, 3H), 1175, 1.09 (d, J = 6.3 Hz, 3H), 0.86 (d, J = 6.7 Hz, 1037, 730 cm.sup.-1 3H), 0.76 (d, J = 6.8 Hz, 3H). 381 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 8.49 (d, J = 7.5 Hz, film) 3385, calcd for C.sub.25H.sub.30F.sub.3N.sub.2O.sub.7, 1H), 8.33 (d, J = 5.5 Hz, 1H), 2964, 527.2000; found, 527.2000 7.16-7.05 (m, 4H), 7.01 (d, J = 5.5 Hz, 1772, 1H), 5.39 (dq, J = 8.2, 6.3 Hz, 1H), 1734, 4.74-4.60 (m, 1H), 3.91 (s, 3H), 2.72 (dd, J = 8.1, 1677, 7.0 Hz, 1H), 2.40 (s, 3H), 1507, 2.15-2.02 (m, 1H), 1.48 (d, J = 7.2 Hz, 3H), 1258, 1.08 (d, J = 6.3 Hz, 3H), 0.88 (d, J = 6.7 Hz,

1199, 1162 cm.sup.-1 3H), 0.74 (d, J = 6.8 Hz, 3H). 382 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (300 MHz, CDCl.sub.3) .delta. 8.38 (d, J = 7.7 Hz, film) 3378, calcd for C.sub.26H.sub.35N.sub.2O.sub.8, 1H), 8.29 (d, J = 5.4 Hz, 1H), 2960, 503.2388; found, 503.2356 7.05-6.98 (m, 2H), 6.96 (d, J = 5.4 Hz, 1733, 1H), 6.87-6.75 (m, 2H), 5.75 (s, 2H), 1675, 5.45-5.30 (m, 1H), 4.80-4.60 (m, 1511, 1H), 3.92 (s, 3H), 3.79 (s, 3H), 2.67 (dd, 1201, J = 8.8, 6.3 Hz, 1H), 2.19-1.98 (m, 1038, 968, 4H), 1.53 (d, J = 7.2 Hz, 3H), 1.09 (d, J = 6.3 Hz, 829 cm.sup.-1 3H), 0.85 (d, J = 6.8 Hz, 3H), 0.75 (d, J = 6.8 Hz, 3H). 383 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 8.55 (s, film) 3378, calcd for C.sub.25H.sub.33N.sub.2O.sub.7, 1H), 8.34 (d, J = 5.4 Hz, 1H), 2960, 473.2282; found, 473.2259 7.07-6.95 (m, 3H), 6.88-6.74 (m, 2H), 1770, 5.37 (dq, J = 8.7, 6.3 Hz, 1H), 1732, 4.75-4.61 (m, 1H), 3.91 (s, 3H), 3.79 (s, 3H), 1675, 2.66 (dd, J = 8.7, 6.4 Hz, 1H), 2.40 (s, 3H), 1511, 2.08 (dq, J = 13.4, 6.7 Hz, 1H), 1.50 (d, 1176, J = 7.2 Hz, 3H), 1.07 (d, J = 6.2 Hz, 1035, 730 cm.sup.-1 3H), 0.84 (d, J = 6.8 Hz, 3H), 0.75 (d, J = 6.8 Hz, 3H). 384 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.56 (s, film) 2963, calcd for C.sub.26H.sub.35N.sub.2O.sub.6, 1H), 8.34 (dd, J = 5.4, 2.0 Hz, 1H), 1772, 471.2416; found, 471.2487 7.19-7.06 (m, 4H), 7.01 (d, J = 5.5 Hz, 1H), 1678, 5.40 (dq, J = 12.1, 6.6 Hz, 1H), 4.72 (p, 1507, J = 7.3 Hz, 1H), 3.91 (s, 3H), 1200, 733 cm.sup.-1 3.39-3.05 (m, 1H), 2.40 (d, J = 1.7 Hz, 3H), 2.33 (d, J = 5.7 Hz, 3H), 1.90 (s, 1H), 1.55-1.18 (m, 5H), 1.04 (d, J = 6.3 Hz, 3H), 1.01-0.71 (m, 6H). 385 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.53 (s, film) 2961, calcd for C.sub.27H.sub.37N.sub.2O.sub.6, 1H), 8.33 (d, J = 5.4 Hz, 1H), 1771, 485.2572; found, 485.2643 7.22-7.05 (m, 4H), 7.01 (d, J = 5.5 Hz, 1H), 1732, 5.43 (dq, J = 8.3, 6.2 Hz, 1H), 4.69 (p, J = 7.3 Hz, 1677, 1H), 3.91 (s, 3H), 3.31 (t, J = 7.6 Hz, 1506, 1H), 2.39 (s, 3H), 2.31 (s, 3H), 1198, 1.63 (d, J = 6.2 Hz, 1H), 1.54-1.17 (m, 1175, 731 cm.sup.-1 6H), 1.17-0.85 (m, 7H), 0.77 (t, J = 7.3 Hz, 3H). 386 IR (thin HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.49 (s, film) 2970, calcd for C.sub.28H.sub.39N.sub.2O.sub.6, 1H), 8.33 (dd, J = 5.4, 2.1 Hz, 1H), 1736, 499.2729; found, 499.2729 7.22-7.05 (m, 4H), 6.99 (d, J = 5.5 Hz, 1H), 1506, 5.39 (dq, J = 9.6, 6.7, 6.2 Hz, 1H), 1210, 733 cm.sup.-1 4.72 (p, J = 7.3 Hz, 1H), 3.89 (s, 3H), 3.30-3.12 (m, 1H), 2.95 (tt, J = 7.0, 6.0 Hz, 1H), 2.33 (s, 3H), 1.88 (d, J = 13.8 Hz, 1H), 1.43 (dd, J = 59.5, 7.0 Hz, 11H), 1.04 (d, J = 6.3 Hz, 3H), 0.83 (qd, J = 15.1, 13.7, 7.1 Hz, 6H). 387 IR (thin film) 2964, HRMS-ESI (m/z) [M + H].sup.+ .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.46 (s, 1681, calcd for C.sub.29H.sub.41N.sub.2O.sub.6, 1H), 8.32 (d, J = 5.5 Hz, 1H), 1505, 513.2883; found, 513.2953 7.17-7.03 (m, 5H), 6.99 (d, J = 5.5 Hz, 1H), 1211, 1111 cm.sup.-1 5.50-5.36 (m, 1H), 4.69 (p, J = 7.3 Hz, 1H), 3.89 (s, 3H), 3.31 (t, J = 7.6 Hz, 1H), 2.94 (p, J = 7.0 Hz, 1H), 2.31 (s, 3H), 1.61 (s, 1H), 1.51-0.94 (m, 15H), 0.90 (t, J = 7.4 Hz, 3H), 0.77 (t, J = 7.3 Hz, 3H). 388 ESIMS m/z 497 ([M + H].sup.+) .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.53 (d, J = 8.0 Hz, 1H), 8.43-8.20 (m, 1H), 7.01 (d, J = 5.5 Hz, 1H), 6.62 (t, J = 9.0 Hz, 2H), 5.65-5.47 (m, 1H), 4.68 (dq, J = 8.3, 7.2 Hz, 1H), 3.91 (s, 3H), 3.19 (t, J = 7.7 Hz, 1H), 2.40 (s, 3H), 2.31-2.13 (m, 1H), 1.49 (d, J = 7.2 Hz, 3H), 1.13 (dt, J = 6.4, 1.2 Hz, 3H), 0.96 (dd, J = 6.7, 3.5 Hz, 3H), 0.77 (dt, J = 6.7, 1.3 Hz, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -105.79 (d, J = 1613.0 Hz), -110.18 (t, J = 6.4 Hz). 389 ESIMS m/z 495 ([M + H].sup.+) .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.51 (d, J = 6.7 Hz, 1H), 8.33 (d, J = 5.4 Hz, 1H), 7.13-6.92 (m, 4H), 5.42 (dqd, J = 7.6, 6.4, 1.2 Hz, 1H), 4.75-4.51 (m, 1H), 3.91 (s, 3H), 3.13 (t, J = 7.7 Hz, 1H), 2.40 (s, 3H), 2.20-2.01 (m, 1H), 1.49 (d, J = 7.2 Hz, 3H), 1.10 (d, J = 6.3 Hz, 3H), 0.93 (d, J = 6.5 Hz, 3H), 0.75 (d, J = 6.7 Hz, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -112.27. 390 ESIMS m/z 495 ([M + H].sup.+) .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.40-8.29 (m, 1H), 7.25-7.08 (m, 3H), 7.06-6.90 (m, 2H), 5.75-5.47 (m, 1H), 4.89-4.39 (m, 1H), 3.91 (s, 3H), 3.62-3.47 (m, 1H), 2.40 (s, 3H), 2.33-2.17 (m, 1H), 1.47 (dd, J = 38.1, 7.2 Hz, 3H), 1.14-1.06 (m, 3H), 0.99 (dd, J = 6.8, 5.6 Hz, 3H), 0.78 (dt, J = 6.9, 2.4 Hz, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -105.07 (d, J = 18.2 Hz). 391 ESIMS m/z 457 ([M + H].sup.+) .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.57 (d, J = 8.1 Hz, 1H), 8.34 (d, J = 5.4 Hz, 1H), 7.22-7.10 (m, 1H), 7.09-6.98 (m, 2H), 6.89 (d, J = 6.0 Hz, 2H), 5.47-5.24 (m, 1H), 4.62 (dp, J = 51.8, 7.2 Hz, 1H), 3.91 (s, 3H), 2.67 (dt, J = 8.7, 6.9 Hz, 1H), 2.40 (s, 3H), 2.33 (d, J = 5.2 Hz, 3H), 2.10 (dt, J = 13.6, 6.8 Hz, 1H), 1.46 (dd, J = 37.4, 7.2 Hz, 3H), 1.09 (d, J = 6.3 Hz, 3H), 0.86 (t, J = 7.0 Hz, 3H), 0.76 (d, J = 6.7 Hz, 3H). 392 ESIMS m/z 479 ([M + H].sup.+) .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.53 (d, J = 7.8 Hz, 1H), 8.33 (d, J = 5.5 Hz, 1H), 7.07-6.78 (m, 4H), 5.45-5.34 (m, 1H), 4.76-4.62 (m, 1H), 3.91 (s, 3H), 3.22-3.08 (m, 1H), 2.40 (s, 3H), 2.09 (dt, J = 13.5, 6.8 Hz, 1H), 1.49 (d, J = 7.1 Hz, 3H), 1.13 (d, J = 6.3 Hz, 3H), 0.95 (t, J = 5.2 Hz, 3H), 0.77 (d, J = 6.7 Hz, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -119.17, -120.97. *Cmpd. No.--Compound Number

TABLE-US-00003 TABLE 3 Biological Testing Rating Scale Rating Table for Fungal Pathogens % Control Rating >80 A .ltoreq.80 B Not Tested C .ltoreq.0 D

TABLE-US-00004 TABLE 4 Biological Activity - PUCCRT and SEPTTR Disease Control in High and Low Volume Applications HV activity at 100 ppm LV activity at 121.5 g/H Cmpd. PUCCRT* SEPTTR* PUCCRT* SEPTTR* No. 1DP* 3DC* 1DP* 3DC* 1DP* 3DC* 1DP* 3DC* 105 A D B B C C C C 106 B D D D C C C C 112 A A A A C C C C 113 A A A A C C C C 114 A B A B C C C C 115 D D B D C C C C 116 A D D B C C C C 117 A D A A C C C C 118 A B B B C C C C 119 A B A A C C C C 120 A D D B C C C C 121 A B B A C C C C 122 A A A B C C C C 123 A A A A C C C C 124 A A A A C C C C 125 A B A A C C C C 126 A B A A C C C C 127 A A A B C C C C 128 B D D B C C C C 129 A D A B C C C C 130 A B B B C C C C 131 A A B B C C C C 132 A A A B C C C C 133 A B A B C C C C 134 B B B B C C C C 135 B A B A C C C C 136 A A A A C C C C 138 A A D D C C C C 139 A B A D C C C C 140 A A D B C C C C 141 B A D A C C C C 142 A A D B C C C C 143 A A A B C C C C 144 A A B A C C C C 145 A A B A C C C C 146 A A B A C C C C 147 A A D B C C C C 148 B A D B C C C C 149 B B B A C C C C 160 C C C C A B B A 161 C C C C A B B A 162 C C C C A A B A 163 C C C C A B B A 164 C C C C A A A A 165 C C C C A A A A 166 C C C C A A B A 167 C C C C A A A A 168 C C C C A A B B 169 C C C C A A B A 170 C C C C A A A A 171 C C C C A A A A 172 C C C C A A A A 173 C C C C A B A A 174 C C C C A A A A 175 C C C C A A A A 176 C C C C A B A A 177 C C C C B D B D 178 C C C C A B D B 179 C C C C A D A A 180 C C C C A B B B 181 C C C C B B B A 182 C C C C A B B A 183 C C C C B B B A 184 C C C C A A A A 185 C C C C A B A A 186 C C C C A A A A 187 C C C C A B A A 188 C C C C A B A A 189 C C C C A B A A 190 C C C C D D D B 191 C C C C D B B B 192 C C C C A B D A 193 C C C C B B D B 194 C C C C B D B A 195 C C C C A A A A 196 C C C C A A A A 197 C C C C A A A A 198 C C C C B D B B 199 C C C C B D A B 200 C C C C B B D B 201 C C C C A B B B 202 C C C C A D B B 203 C C C C B B B B 204 C C C C A B D B 205 C C C C A D B B 206 C C C C B D B B 207 C C C C A B B A 208 C C C C B B D B 209 C C C C D D B B 210 C C C C B D A B 211 B D B B D D B D 212 A B B A B D D D 213 C C C C B D B B 214 C C C C A A A A 215 C C C C A A A A 216 C C C C A A A A 217 C C C C A A A A 218 C C C C A B A B 219 C C C C A A B A 220 C C C C A A A A 221 C C C C B B B A 222 C C C C A B A A 223 C C C C B B A A 224 C C C C B B B D 225 C C C C A B A A 226 C C C C B B B B 227 C C C C A A A A 228 C C C C A B A B 229 C C C C A B A A 230 C C C C A A A B 231 C C C C B B B B 232 C C C C A A A B 233 C C C C B B A A 234 C C C C A B B B 235 C C C C A B B B 236 C C C C B B B B 237 C C C C A A B B 238 C C C C B B B B 239 C C C C A A A B 240 C C C C A A B A 241 C C C C B B D A 242 C C C C A A A A 243 C C C C A B D B 244 C C C C A A A B 245 C C C C A A B C 246 C C C C A A A C 247 C C C C A A B C 248 C C C C B B B C 249 C C C C A A B C 250 C C C C A A A C 251 C C C C A A B C 252 C C C C A B B C 253 C C C C A A B C 254 C C C C A A A C 255 C C C C A A B C 256 C C C C A A A C 257 C C C C A A A C 258 C C C C A B B C 259 C C C C A A B C 260 C C C C A A A C 261 C C C C A B B B 262 C C C C A B B B 263 C C C C A A B A 264 C C C C A A B B 317 A A B B C C C C 318 A A B B C C C C 319 B B B B C C C C 320 B B B B C C C C 321 A A B B C C C C 322 A A B B C C C C 323 A A B A C C C C 324 A A B B C C C C 325 A A A B C C C C 326 A A B A C C C C 327 A A B A C C C C 328 A A A A C C C C 329 A A B B C C C C 330 A A B B C C C C 331 B B B B C C C C 332 B B B B C C C C 333 A B B B C C C C 334 A A B D C C C C 335 A A A B C C C C 336 A B B B C C C C 337 A A B D C C C C 338 A A B B C C C C 339 C C C C 340 C C C C C C C C 341 A A A A C C C C 342 C C C C C C C C 343 A A A A C C C C 344 C C C C C C C C 345 C C C C C C C C 346 C C C C A A B B 347 C C C C A B A A 348 C C C C A B B B 349 C C C C A B B B 350 C C C C A A B B 351 C C C C A B A B 352 C C C C A B B B 353 C C C C B B B B 354 C C C C A B A A 355 C C C C A B A A 356 C C C C A B A A 357 C C C C A A A A 358 C C C C A B B B 359 C C C C A A B A 360 C C C C A A B A 361 C C C C A B B B 362 C C C C A A A A 363 C C C C A A B B 364 C C C C A B B B 365 C C C C A A A A 366 C C C C A A B B 367 C C C C A A A B 368 C C C C B D B B 369 C C C C A B B B 370 C C C C B D B B 371 C C C C C C C C 372 C C C C C C C C 373 C C C C A B A A 374 C C C C A B A A 375 C C C C A A B A 376 C C C C A B B B 377 C C C C A B B B 378 C C C C A A A A 379 C C C C A B B B 380 C C C C A A B B 381 C C C C A B A A 382 C C C C A A B A 383 C C C C A B B B 384 C C C C A A A A 385 C C C C A A A A 386 C C C C A A B A 387 C C C C A B B A 388 C C C C A A A A 389 C C C C A A A A 390 C C C C A A A A 391 C C C C A B B B 392 C C C C A A B A *Cmpd. No.--Compound Number *PUCCRT--Wheat Brown Rust (Puccinia triticina) *SEPTTR--Wheat Leaf Blotch (Zymoseptoria tritici) *1DP--1 Day Protectant *3DC--3 Day Curative *ppm--Parts Per Million

TABLE-US-00005 TABLE 5 Biological Activity - High Volume Disease Control at 25 ppm PHAKPA* Cmpd. No.* 1DP* 3DC* 162 A B 164 A B 177 A D 178 D B 179 B B 180 B B 181 D B 182 B B 183 B B 184 A B 185 A B 186 A A 187 A B 188 A A 189 A B 190 B B 191 B D 192 A B 193 B B 194 B B 195 A B 196 A B 197 A A 198 B B 199 B B 200 B D 201 B D 202 B D 203 A D 204 B D 205 B D 206 B D 207 A D 208 B D 209 B D 210 B B 211 B D 212 B B 213 D D 214 A B 215 A A 216 A A 217 A A 218 B B 219 A A 220 A A 221 B B 222 A B 223 B D 224 B D 225 A B 226 B D 227 A B 228 A B 229 A B 230 A B 231 A B 232 A A 233 B B 234 A D 235 A B 236 A B 237 A A 238 B B 239 A A 240 A B 241 B B 242 A B 243 A B 244 A B 346 A B 347 A A 348 A B 349 A B 350 A A 351 A B 352 A B 353 A B 354 A A 355 A A 356 A A 357 A A 358 A B 359 A A 360 A A 361 A A 362 A A 363 A A 364 A A 365 A A 366 A B 367 A A 368 B B 369 B B 370 B B 371 A A 372 A A 373 A A 374 A B 375 A A 376 A B 377 B B 378 B B 379 B B 380 B B 381 B B 382 A B 383 A B *Cmpd. No.--Compound Number *PHAKPA--Asian Soybean Rust (Phakopsora pachyrhizi) *1DP--1 Day Protectant *3DC--3 Day Curative

TABLE-US-00006 TABLE 6 Biological Activity - Disease Control in 1DP* test at 100 ppm Cmpd. No.* ALTESO* CERCBE* COLLLA* LEPTNO* 186 A A D A 187 B A A B 216 B A B A 217 B A D A 218 D A B A 219 B A B A 220 B A B A 354 B A A A 355 A A A A 356 A A B A 357 B A A A 359 B A A A 363 D A B B 364 B A A B 371 B A A A 372 A A A A 373 B A A A 374 B A B A 375 B A A A *Cmpd. No.--Compound Number *ALTESO--Tomato Early Blight (Alternaria solani) *CERCBE--Leaf Spot of Sugar Beets (Cercospora beticola) *COLLLA--Cucumber Anthracnose (Glomerella lagenarium; Anamorph: Colletotricum lagenarium) *LEPTNO--Wheat Glume Blotch (Parastagonospora nodorum)

TABLE-US-00007 TABLE 7 Biological Activity - Disease Control in 1DP* Test at 100 ppm Cmpd. No.* PSPECU* PYRIOR* RHYNSE* UNCINE* 186 B A B A 187 D A A A 216 B A B A 217 D A B A 218 D A B A 219 B A B A 220 D A B A 354 A B B A 355 B B B A 356 B B B A 357 B B B A 359 B A A A 363 D A B A 364 B A B A 371 B B B A 372 A B B A 373 B B B A 374 B B B A 375 B A B A *Cmpd. No.--Compound Number *PSPECU--Cucumber Downy Midlew (Pseudoperonospora cubensis) *PYRIOR--Rice Blast (Magnaporthe grisea; Anamorph: Pyricularia oryzae) *RHYNSE--Barley Scald (Rhyncosporium secalis) *UNCINE--Grape Powdery Mildew (Uncinula necator) *1DP--1 Day Protectant

Claims

1. A compound of Formula I ##STR00453## wherein: X is hydrogen or C(O)R.sub.5; Y is hydrogen, C(O)R.sub.5, or Q; Q is ##STR00454## wherein Z is N or N.sup.+.fwdarw.O.sup.- and W is O or S; R.sub.1 is hydrogen or alkyl, substituted with 0, 1 or multiple R.sub.8; R.sub.2 is methyl; R.sub.3 and R.sub.3' are independently chosen from C.sub.2-C.sub.6 alkyl, C.sub.3-C.sub.6 cycloalkyl, aryl or heteroaryl, each optionally substituted with 0, 1 or multiple R.sub.8; Alternatively, R.sub.3 and R.sub.3' may be taken together to form a 3-6 membered saturated or partially saturated carbocycle or heterocycle, optionally substituted with 0, 1 or multiple R.sub.8; R.sub.4 is chosen from aryl or heteroaryl, each optionally substituted with 0, 1 or multiple R.sub.8; R.sub.5 is chosen from alkoxy or benzyloxy, each optionally substituted with 0, 1, or multiple R.sub.8; R.sub.6 is chosen from hydrogen, alkoxy, or halo, each optionally substituted with 0, 1, or multiple R.sub.8; R.sub.7 is chosen from hydrogen, --C(O)R.sub.9, or --CH.sub.2OC(O)R.sub.9; R.sub.8 is chosen from hydrogen, alkyl, aryl, acyl, halo, alkenyl, alkynyl, alkoxy, cyano, or heterocyclyl, each optionally substituted with 0, 1, or multiple R.sub.10, R.sub.9 is chosen from alkyl, alkoxy, or aryl, each optionally substituted with 0, 1, or multiple R.sub.8; R.sub.10 is chosen from hydrogen, alkyl, aryl, acyl, halo, alkenyl, alkoxy, or heterocyclyl; and R.sub.11 is chosen from hydrogen or alkyl, each substituted with 0, 1 or multiple R.sub.8.

2. The compound according to claim 1, wherein X and Y are hydrogen.

3. The compound according to claim 2, wherein R.sub.1 and R.sub.11 are independently chosen from hydrogen or alkyl.

4. The compound according to claim 2, wherein R.sub.3 and R.sub.3' are independently chosen from C.sub.2-C.sub.6 alkyl or taken together to form a 3-6 membered saturated carbocycle, each optionally substituted with 0, 1 or multiple R.sub.8.

5. The compound according to claim 2, wherein R.sub.4 is aryl, optionally substituted with 0, 1 or multiple R.sub.8.

6. The compound according to claim 2, wherein R.sub.1 and R.sub.11 are independently chosen from hydrogen or alkyl, R.sub.3 and R.sub.3' are independently chosen from C.sub.2-C.sub.6 alkyl or taken together to form a 3-6 membered saturated carbocycle, each optionally substituted with 0, 1 or multiple R.sub.8, and R.sub.4 is aryl, optionally substituted with 0, 1 or multiple R.sub.8.

7. The compound according to claim 1, wherein X is C(O)R.sub.5 and Y is hydrogen.

8. The compound according to claim 7, wherein R.sub.1 and R.sub.11 are independently chosen from hydrogen or alkyl.

9. The compound according to claim 7, wherein R.sub.3 and R.sub.3' are independently chosen from C.sub.2-C.sub.6 alkyl or taken together to form a 3-6 membered saturated carbocycle, each optionally substituted with 0, 1 or multiple R.sub.8.

10. The compound according to claim 7, wherein R.sub.4 is aryl, optionally substituted with 0, 1 or multiple R.sub.8.

11. The compound according to claim 7, wherein R.sub.1 and R.sub.11 are independently chosen from hydrogen or alkyl, R.sub.3 and R.sub.3' are independently chosen from C.sub.2-C.sub.6 alkyl or taken together to form a 3-6 membered saturated carbocycle, each optionally substituted with 0, 1 or multiple R.sub.8, and R.sub.4 is aryl, optionally substituted with 0, 1 or multiple R.sub.8.

12. The compound according to claim 1, wherein X is hydrogen and Y is Q.

13. The compound according to claim 12 wherein Z is N.

14. The compound according to claim 13 wherein W is O.

15. The compound according to claim 14, wherein R.sub.6 is alkoxy.

16. The compound according to claim 15, wherein R.sub.7 is hydrogen.

17. The compound according to claim 16, wherein R.sub.1 and R.sub.11 are independently chosen from hydrogen or alkyl.

18. The compound according to claim 16, wherein R.sub.3 and R.sub.3' are independently chosen from C.sub.2-C.sub.6 alkyl or taken together to form a 3-6 membered saturated carbocycle, each optionally substituted with 0, 1 or multiple R.sub.8.

19. The compound according to claim 16, wherein R.sub.4 is aryl, optionally substituted with 0, 1 or multiple R.sub.8.

20. The compound according to claim 16, wherein R.sub.1 and R.sub.11 are independently chosen from hydrogen or alkyl, R.sub.3 and R.sub.3' are independently chosen from C.sub.2-C.sub.6 alkyl or taken together to form a 3-6 membered saturated carbocycle, each optionally substituted with 0, 1 or multiple R.sub.8, and R.sub.4 is aryl, optionally substituted with 0, 1 or multiple R.sub.8.

21. The compound according to claim 15, wherein R.sub.7 is chosen from --C(O)R.sub.9, or --CH.sub.2OC(O)R.sub.9.

22. The compound according to claim 21, wherein R.sub.1 and R.sub.11 are independently chosen from hydrogen or alkyl.

23. The compound according to claim 21, wherein R.sub.3 and R.sub.3' are independently chosen from C.sub.2-C.sub.6 alkyl or taken together to form a 3-6 membered saturated carbocycle, each optionally substituted with 0, 1 or multiple R.sub.8.

24. The compound according to claim 21, wherein R.sub.4 is aryl, optionally substituted with 0, 1 or multiple R.sub.8.

25. The compound according to claim 21, wherein R.sub.1 and R.sub.11 are independently chosen from hydrogen or alkyl, R.sub.3 and R.sub.3' are independently chosen from C.sub.2-C.sub.6 alkyl or taken together to form a 3-6 membered saturated carbocycle, each optionally substituted with 0, 1 or multiple R.sub.8, and R.sub.4 is aryl, optionally substituted with 0, 1 or multiple R.sub.8.

26. A composition for the control of a fungal pathogen including mixtures of at least one of the compounds of claim 1 and another pesticide including fungicides, insecticides, nematocides, miticides, arthropodicides, bactericides and combinations thereof.

27. A composition for the control of a fungal pathogen including mixtures of at least one of the compounds of claim 16 and another pesticide including fungicides, insecticides, nematocides, miticides, arthropodicides, bactericides and combinations thereof.

28. A composition for the control of a fungal pathogen including mixtures of at least one of the compounds of claim 21 and another pesticide including fungicides, insecticides, nematocides, miticides, arthropodicides, bactericides and combinations thereof.

29. A method for the control and prevention of fungal attack on a plant, the method including the step of: applying a fungicidally effective amount of at least one of the compounds of claim 1 to at least one of the plant, an area adjacent to the plant, soil adapted to support growth of the plant, a root of the plant, and foliage of the plant.

30. A method for the control and prevention of fungal attack on a plant, the method including the step of: applying a fungicidally effective amount of at least one of the compounds of any of claim 26 to at least one of the plant, an area adjacent to the plant, soil adapted to support growth of the plant, a root of the plant, and foliage of the plant.