RU2797810C2 - Picolinamide compounds with fungicidal activity - Google Patents

Abstract

FIELD: fungicidal compounds.

SUBSTANCE: invention relates to a compound of formula I which has fungicidal activity. The invention also relates to a method for controlling and preventing fungal infestation of a plant, comprising the step of applying an effective fungicidal amount of said compound to at least one of the plant, an area adjacent to the plant, soil adapted to support plant growth, a plant root, and plant foliage.

EFFECT: compound with fungicidal activity.

2 cl, 7 tbl, 31 ex

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to U.S. Provisional Patent Applications Serial Nos. 62/098120, filed December 30, 2014, and 62/098122, filed December 30, 2014, which are expressly incorporated by reference herein.

BACKGROUND AND SUMMARY

[0002] Fungicides are compounds, natural or synthetic in origin, that act to protect and/or treat plants from damage caused by agriculturally relevant fungi. In general, one fungicide cannot be used in all situations. Therefore, research is being done to obtain fungicides that can be more effective, easier to use, and less expensive.

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

[0004] One of the embodiments of the present disclosure may include compounds of formula I:

in which: X represents hydrogen or C(O)R ₅ ; Y is hydrogen, C(O)R ₅ or Q; Q represents

where: Z is N or CH;

R ₁ is hydrogen or alkyl, each optionally substituted with 0, 1 or more R ₈ ; R ₂ is methyl;

R ₃ is selected from aryl or heteroaryl, each optionally substituted with 0, 1 or more R ₈ ;

R ₄ is selected from hydrogen, halo, hydroxyl, alkyl or alkoxy;

R ₅ is selected from alkoxy or benzyloxy, each optionally substituted with 0, 1 or more R ₈ ;

R ₆ is selected from hydrogen, alkoxy or halo, each optionally substituted with 0, 1 or more R ₈ ;

R ₇ is selected from hydrogen, -C(O)R ₉ , or -CH ₂ OC(O)R ₉ ;

R ₈ is selected from hydrogen, alkyl, aryl, acyl, halo, alkenyl, alkynyl, alkoxy, cyano or heterocyclyl, each optionally substituted with 0, 1 or more R ₁₀ ;

R ₉ is selected from alkyl, alkoxy or aryl, each optionally substituted with 0, 1 or more R ₈ ;

R ₁₀ is selected from hydrogen, alkyl, aryl, acyl, halo, alkenyl, alkoxy or heterocyclyl;

R ₁₁ is selected from hydrogen or alkyl substituted with 0, 1 or more R ₈ ;

R ₁₂ is selected from aryl or heteroaryl, each optionally substituted with 0, 1 or more R ₈ .

[0005] Another embodiment of the present disclosure may include a fungicidal composition for controlling or preventing fungal infestation that contains the compounds described above and a phytologically acceptable carrier material.

[0006] Yet another embodiment of the present disclosure may include a method of controlling or preventing fungal infestation on a plant, the method comprising 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 the area adjacent to the plant.

[0007] Those skilled in the art will appreciate that the following terms may include the characteristic "R" groups within their definitions, for example, "the term alkoxy refers to a -OR substituent." It is also understood that within the definitions for the following terms, these "R" groups are included for illustrative purposes and should not be construed as being limited or to be limited by substitutions in Formula I.

[0008] The term "alkyl" refers to a branched, straight 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 etc.

[0009] The term "alkenyl" refers to a branched, straight 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.

[0010] The term "alkynyl" refers to a straight or branched carbon chain containing one or more triple bonds, including but not limited to propynyl, butynyl, and the like.

[0011] The terms "aryl" and "Ar" refer to any aromatic ring, mono- or bicyclic, containing 0 heteroatoms.

[0012] The term "heterocyclyl" refers to any aromatic or non-aromatic ring, mono- or bicyclic, containing one or more heteroatoms.

[0013] The term "alkoxy" refers to the -OR substituent.

[0014] The term "acyloxy" refers to a -OC(O)R substituent.

[0015] The term "cyano" refers to a -C=N substituent.

[0016] The term "hydroxyl" refers to the -OH substituent.

[0017] The term "amino" refers to the substituent -N(R) ₂ .

[0018] The term "arylalkoxy" refers to -O(CH ₂ ) _n Ar, where n is an integer selected from the list of 1, 2, 3, 4, 5, or 6.

[0019] The term "haloalkoxy" refers to the substituent -OR-X, in which X represents Cl, F, Br or I or any combination thereof.

[0020] The term "haloalkyl" refers to alkyl that is substituted with Cl, F, I, or Br, or any combination thereof.

[0021] The term "halogen" or "halo" refers to one or more halogen atoms, which are defined as F, Cl, Br, and I.

[0022] The term "nitro" refers to a -NO ₂ substituent.

[0023] The term thioalkyl refers to the -SR substituent.

[0024] Throughout the disclosure, reference to compounds of formula I is understood to also include all stereoisomers, eg, diastereomers, enantiomers, and mixtures thereof. In another embodiment, formula I is understood to also include its salts or hydrates. Exemplary salts include, but are not limited to, hydrochloride, hydrobromide, hydroiodide, trifluoroacetate, and trifluoromethanesulfonate.

[0025] Also, those skilled in the art will appreciate that additional substitution is acceptable, unless otherwise noted, as long as the bonding and strain energy rules are met and the product still exhibits fungicidal activity.

[0026] Another embodiment of the present disclosure is the use of a compound of formula I to protect a plant from attack by a phytopathogenic organism or to treat a plant infected by a phytopathogenic organism, which comprises applying a compound of formula I or a composition containing the compound to soil, to a plant, part plants, foliage and/or roots.

[0027] Additionally, another embodiment of the present disclosure is a composition that can be used to protect a plant from attack by a phytopathogenic organism and/or treat a plant infected by a phytopathogenic organism, which contains a compound of formula I and a phytologically acceptable carrier material.

DETAILED DESCRIPTION

[0028] the Compounds of the present disclosure can be used in any of the various known ways, either in the form of compounds or in the form of compositions containing compounds. For example, the compounds can be applied to the roots or foliage of plants to control various fungi without compromising the commercial value of the plants. The materials may be applied in the form of any of the commonly used types of formulations, such as solutions, powders, wettable powders, bulk concentrate, or emulsifiable concentrates.

[0029] Preferably, the compounds of the present disclosure are administered in the form of a formulation that contains one or more compounds of formula I with a phytologically acceptable carrier. Concentrated formulations may be dispersed in water or other application liquids, or the formulations may be powdered or granular and may then be applied without further processing. The compositions can be obtained in accordance with procedures that are standard in the field of agricultural chemistry.

[0030] The present disclosure contemplates all excipients with which one or more compounds can be formulated for delivery and use as a fungicide. Typically, the formulations are applied as aqueous suspensions or emulsions. Such suspensions or emulsions can be prepared from water-soluble, water-suspendable or emulsifiable formulations which are solids commonly known as wettable powders; or liquids commonly known as emulsifiable concentrates, aqueous suspensions or suspension concentrates. It is readily appreciated that any material to which these compounds can be added can be used, as long as it provides the desired utility without significant interaction with the antifungal activity of these compounds.

[0031] Wettable powders that can be compacted to form water-dispersible granules contain an intimate mixture of one or more 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 from about 25 percent by weight to about 75 percent by weight. In preparing wettable powder formulations, the compounds may be compounded with any finely divided solid such as prophyllite, talc, chalk, thorns, fuller's earth, bentonite, attapulgite, starch, casein, gluten, montmorillonite clays, diatomaceous earths, purified silicates, or the like. . In such operations, the finely divided and surfactants are typically mixed with the compound(s) and ground.

[0032] Emulsifiable concentrates of compounds of Formula I may be at a convenient concentration, such as from about 1 percent by weight to about 50 percent by weight of the compound, in a suitable liquid, based on the total weight of the concentrate. The compounds can 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 can be diluted with water and oil to form spray mixtures in the form of oil-in-water emulsions. Effective organic solvents include aromatics, in particular the naphthalene and olefinic portions of high boiling oils such as heavy aromatic naphtha. Other organic solvents may also be used, for example, terpene solvents including rosin derivatives, aliphatic ketones such as cyclohexanone, and complex alcohols such as 2-ethoxyethanol.

[0033] Those skilled in the art can easily identify emulsifiers that can be usefully used herein, which include various non-ionic, anionic, cationic, and amphoteric emulsifiers, or a mixture of two or more emulsifiers. Examples of non-ionic emulsifiers that can be used in the preparation of emulsifiable concentrates include polyalkylene glycol ethers and condensation products of alkyl and arylphenols, aliphatic alcohols, aliphatic amines or fatty acids with ethylene oxide, propylene oxides such as ethoxylated alkylphenols and carboxylic esters solubilized using a polyol. or polyoxyalkylene. Cationic emulsifiers include quaternary ammonium compounds and fatty amine salts. Anionic emulsifiers include oil-soluble salts (eg, calcium) of alkylarylsulfonic acids, oil-soluble salts or ethers of sulfated polyglycols, and suitable ether salts of phosphated polyglycols.

[0034] Representative organic liquids that can be used in the preparation of emulsifiable concentrates of the compounds of the present disclosure are aromatic liquids such as xylene, propylbenzene fractions; or mixed naphthalene fractions, mineral oils, substituted aromatic organic liquids such as dioctyl phthalate; kerosene; dialkylamides of various fatty acids, in particular fatty glycol dimethylamides, and glycol derivatives such as n-butyl ether, ethyl ether or diethylene glycol methyl ether, triethylene glycol methyl ether, petroleum fractions or hydrocarbons such as mineral oil, aromatic solvents, paraffin oils and the like; vegetable oils such as soybean oil, rapeseed oil, olive oil, castor oil, sunflower seed oil, coconut oil, corn oil, cottonseed oil, linseed oil, palm oil, peanut oil, safflower oil, sesame oil, tung oil, etc. P.; esters of the aforementioned vegetable oils; and so on. Mixtures of two or more organic liquids can also be used in the preparation of an emulsifiable concentrate. Organic liquids include xylene and propylbenzene fractions, with xylene being the most preferred in some cases. The surfactant dispersant is typically used in liquid formulations and in an amount of 0.1 to 20 percent by weight based on the total weight of the dispersant with one or more of the compounds. The compositions may also contain other compatible additives, such as plant growth regulators and other biologically active compounds used in agriculture.

[0035] Aqueous suspensions include suspensions of one or more water-insoluble compounds of Formula I dispersed in an aqueous vehicle at a concentration in the range of from about 1 to about 50 percent by weight, 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 milled material in a vehicle consisting of water and surfactants selected 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.

[0036] The compounds of formula I can also be used in the form of granular formulations, which are particularly useful when applied to the soil. Granular formulations generally contain from about 0.5 to about 10 percent by weight, based on the total weight of the granular formulation, of the compound(s) dispersed in an inert carrier that consists wholly or in large part of a coarsely divided inert material such as attapulgite. , bentonite, diatomaceous earth, clay or similar inexpensive material. Such formulations are generally prepared by dissolving the compounds in a suitable solvent and applying them to a granular carrier which is in the form of suitable particle sizes ranging from about 0.5 to about 3 mm. A suitable solvent is one in which the compound is substantially or completely soluble. Such formulations can also be prepared by preparing a dough or paste from a carrier and a compound and a solvent and grinding and drying to obtain the desired granular particles.

[0037] Powders containing compounds of formula I can be prepared by intimately mixing one or more compounds in powder form with a suitable powdered agricultural carrier such as, for example, kaolin clay, crushed volcanic rock, and the like. The powders may suitably contain from about 1 to about 10 weight percent compounds, based on the total weight of the powder.

[0038] The formulations may further contain adjuvant surfactants to enhance the deposition, wetting, and penetration of the compounds into the target crop and organism. These adjuvant surfactants can optionally be used as a formulation component or as a tank mix. The amount of adjuvant surfactant typically ranges from 0.01 to 1.0 percent by volume, based on the volume of water sprayed, preferably from 0.05 to 0.5 percent by volume. Suitable adjuvant surfactants include, but are not limited to, ethoxylated nonylphenols, ethoxylated synthetic or natural alcohols, ester or sulfosuccinic acid salts, ethoxylated organosilicon compounds, ethoxylated fatty amines, mixtures of surfactants with mineral or vegetable oils, concentrated oils agricultural crops (mineral oil (85%) + emulsifiers (15%); nonylphenol ethoxylate; benzylcocoalkyldimethyl quaternary ammonium salt; a mixture of petroleum hydrocarbon, alkyl esters, organic acid and an anionic surfactant; C ₉ -C ₁₁ alkyl polyglycoside; phosphated alcohol ethoxylate; natural primary alcohol ethoxylate (C ₁₂ -C ₁₆ ); di-sec-butylphenol EO-PO block copolymer; methyl-terminated polysiloxane; nonylphenol ethoxylate + urea ammonium nitrate; emulsified methylated seed oil; tridecyl alcohol ethoxylate (synthetic) (8EO); tallow amine ethoxylate (15 EO); PEG(400) dioleate-99. The formulations may also include oil-in-water emulsions such as those disclosed in US Patent Application Serial No. 11/495,228, the disclosure of which is expressly incorporated herein by reference.

[0039] 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, which are compatible with the compounds of the present disclosure in the medium chosen for use and are not antagonistic to the activity of these compounds. Accordingly, in such embodiments, other pesticidal compounds are used as an additional toxic agent for the same or a different pesticidal use. The compounds of formula I and the pesticidal compound in combination may generally be present in a weight ratio of from 1:100 to 100:1.

[0040] The compounds of the present disclosure can also be combined with other fungicides to form fungicidal mixtures and synergistic mixtures thereof. The fungicidal compounds of the present disclosure are often used in combination with one or more other fungicides in order to control a wider range of undesirable diseases. When used in combination with another 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, amethoctradine, amisulbrom, antimycin, Ampelomyces quisqualis, aconazole, azoxystrobin, Bacillus subtilis, Bacillus subtilis strain QST713, benalaxyl, benomyl, benthiavalicarb- isopropyl , benzovindiflupyr, benzyl aminobenzene sulfonate (BABS) salt, bicarbonates, biphenyl, bismertiazole, bitertanol, bixaphene, blastcidin-S, borax, bard mix, boscalid, bromuconazole, bupirimate, calcium polysulfide, captafol, captan, carbendazim, carboxin, carpropamide, carvone , chlazaphenone, chloroneb, chlorthalonil, chlosolinate, hyperparasite fungus Coniothyrium minitans , copper hydroxide, copper octanoate, copper oxychloride, copper sulfate, copper sulfate (tribasic), cumoxystrobin, copper oxide, cyazofamide, cyflufenamid, cymoxanil, cyproconazole, cyprodinil, dazo meth , debacarb, diammonium ethylenebis-(dithiocarbamate), dichlorofluanid, dichlorphen, diclocymet, diclomesin, dichloran, diethofencarb, difenoconazole, diphenzoquat ion, diflumetorim, dimetromorph, dimoxystrobin, diniconazole, diniconazole-M, dinobuton, dinocap, diphenylamine, dipimethitrone, di tianon, dodemorph , dodemorph acetate, dodin, dodine free base, edifenphos, enestrobin, enestroburin, enoxastrobin, epoxiconazole, ethoboxam, ethoxyquin, etridiazol, famoxadone, fenamidone, phenaminostrobin, fenarimol, fenbuconazole, fenfuram, fenhexamide, fenoxanil, fenpiclonil, fenpropymorph, fenpro pymorph, phenpyrazamine, fentin, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, fluphenoxystrobin, flumorph, fluopicolide, fluopyram, fluorimide, fluoxastrobin, fluquinconazole, fluzilazole, flusulfamide, flutianil, flutolanil, flutriafol, fluxapiroxade, folpet, formaldehyde, fosetil, fosetil- aluminium, fuberidazole, furalaxyl, furametpyr, guasatin, guasatin acetates, GY-81, hexachlorobenzene, hexaconazole, hymexazole, imazalil, imazalyl sulfate, imibenconazole, iminoctadine, iminoctadine triacetate, iminoctadine tri(albesilate), iodocarb, ipconazole, ipfenpyrazole he, iprobenfos, iprodione , iprovalicarb, isofetamide, isoprothiolane, isopyrazam, isothianil, kasugamycin, kasugamycin hydrochloride hydrate, kresoxim-methyl, laminarin, mancopper, mancozeb, mandestrobin, mandipropamide, maneb, mefenoxam, mepanipyrim, mepronil, meptyl-dinocap, mercury(I) chloride, oxide mercury, mercury (II) chloride, metalaxyl, metalaxyl-M, metam, metam-ammonium, metam-potassium, metam-sodium, metconazole, metasulfocarb, methyl iodide, methylisothiocyanate, metiram, methominostrobin, metrafenone, mildiomycin, myclobutanil, nabam, nitrotal- isopropyl, nuarimol, octilinone, ofuras, oleic acid (fatty acids), orysastrobin, oxadixyl, oxathiapiproline, oxin-copper, oxpoconazole fumarate, oxycarboxin, pefurazoate, penconazole, pencicuron, penflufen, pentachlorophenol, pentachlorophenyl laurate, penthiopyrad, phenylmercury acetate, phosphonic acid , phthalide, picarbutrazox, picoxystrobin, polyoxin B, polyoxins, polyoxorim, potassium bicarbonate, potassium hydroxyquinoline sulfate, probenazole, prochloraz, procymidone, propamocarb, propamocarb hydrochloride, propiconazole, propineb, proquinazid, prothioconazole, pyraclostrobin, piracosystrobin, picoxystrobin, pyraziflumide, pyrazof os, pyribencarb, pyributicarb, pyrifenox, pyrimethanil, pyriophenone, pyrisoxazole, pyrochilon, quinoclamin, quinoxyfen, quintozen, Reynoutria sachalinensis extract, sedaxan, silthiopham, simeconazole, sodium 2-phenylphenoxide, sodium bicarbonate, sodium pentachlorophenoxide, spiroxamine, sulfur, SYP-Z 048, tar oils, tebuconazole, tebufloquine, teknazen, tetraconazole, thiabendazole, thifluzamide, thiophanate-methyl, thiram, thiadinil, tolclofos-methyl, tolprocarb, tolylfluanid, triadimefon, triadimenol, triazoxide, triclopipicarb, tricyclazole, tridemorph, trifloxitrobin, triflumizole, tri forin, triticonazole, validamycin, valifenalate, falifenal, vinclozolin, cineb, cyram, 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-dithiin 1,1,4,4-tetraoxide, 2-methoxyethylmercury acetate, 2-methoxyethylmercury chloride, 2 -methoxyethylmercury silicate, 3-(4-chlorophenyl)-5-methylrhodanine, 4-(2-nitroprop-1-enyl)phenylthiocyanate, ampropylphos, anilazine, azithiram, barium polysulfide, Bayer 32394, benodanil, benquinox, bentalurone, benzamacryl, benzamacryl -isobutyl, benzamorph, binapacryl, bis(methylmercury) sulfate, bis(tributyltin) oxide, butiobate, calcium copper zinc cadmium chromate sulfate, carbamorph, CECA, chlobentiazone, chloraniformmethane, chlorphenazole, chlorquinox, climbazole, copper bis(3-phenyl salicylate), copper zinc chromate, kufraneb, hydrazinium copper sulfate, cuprobam, cicaframide, cypendazole, cyprofuram, decafentine, dichlon, dichlozolin, diclobutrazol, dimethirimol, dinoctone, dinosulfone, dinoterbon, dipyrithione, dithalymphos, dodicine, drazoxolone, EBP, ESBP, etaconazole, etem , etirim, fenaminosulf, fenapanil, fenitropan, fluotrimazole, furcarbanil, funconazole, furconazole-cis, furmecyclox, furofanate, glyodine, griseofulvin, galacrinate, Hercules 3944, hexylthiophos, ICIA0858, isopamphos, isovaledione, mebenil, mecarbinzid , metazoxolone, metfuroxam, methylmercury dicyandiamide, metsulfowax, milneb, mucochloride anhydride, myclozolin, N-3,5-dichlorophenylsuccinimide, N-3-nitrophenylitaconimide, natamycin, N-ethylmercury-4-toluenesulfonanilide, nickel bis(dimethyldithiocarbamate), OCH, phenylmercury dimethyldithiocarbamate, phenylmercury nitrate, phosdifene, anti ocarb , prothiocarb hydrochloride, pyracarbolide, pyridinitrile, pyroxychlor, pyroxyfur, quinacetol, quinacetol sulfate, quinazamide, quinconazole, rabenzazole, salicylanilide, SSF-109, sultropene, tecoram, thiadifluoro, thithiofen, thiochlorfenprim, thiophanate, thioquinox, thioximide, triamiphos, triarimol, triazbutyl , triclamide, urbacid, zarylamide, and any combination thereof.

[0041] Additionally, the compounds described herein can be combined with other pesticides, which include insecticides, nematicides, miticides, arthropodicides, bactericides, or combinations thereof, which are compatible with the compound of the present disclosure in the medium chosen for use and are not antagonistic for the activity of these compounds to form pesticide mixtures and their synergistic mixtures. The fungicidal compounds of the present disclosure may be used in combination with one or more other pesticides in order to control a broader range of unwanted pests. When used in combination with other pesticides, the presently claimed compounds may be formulated with another pesticide(s), tank mixed with another pesticide(s), or applied sequentially with another pesticide(s). Typical insecticides include, but are not limited to: 1,2-dichloropropane, abamectin, acephate, acetamiprid, acetion, acetoprol, acrinathrine, acrylonitrile, afidpyropene, alanicarb, aldicarb, aldoxycarb, aldrin, allethrin, allosamidin, allixicarb, alpha-cypermethrin, alpha -ecdysone, alpha-endosulfan, amidithione, aminocarb, amiton, amiton oxalate, amitraz, anabasin, atidathione, azadirachtin, azamethifos, azinphos-ethyl, azinphos-methyl, azotoate, barium hexafluorosilicate, bartrin, bendiocarb, benfuracarb, bensultap, beta- cyfluthrin , beta-cypermethrin, bifenthrin, bioalletrin, bioetanometrin, biopermethrin, bistrifluron, borax, boric acid, broflanilide, bromfenvinphos, bromocyclene, bromine-DDT, bromophos, bromophos-ethyl, bufencarb, buprofezin, butacarb, butathiophos, butocarboxym, butonate, butoxy carboxy, cadusafos, calcium arsenate, calcium polysulfide, camphechlor, carbanolate, carbaryl, carbofuran, carbon disulfide, carbon tetrachloride, carbofenotion, carbosulfan, cartap, cartap hydrochloride, chlorantraniliprole, chlorbicyclene, chlordane, chlordecone, chlordimeform, chlordimeform hydrochloride, chlorethoxyphos, chlorfenapyr, chlorphenvinphos, chlorine fluazuron , chlormephos, chloroform, chlorpicrin, chlorphoxim, chlorprazophos, chlorpyrifos, chlorpyrifos-methyl, chlorthiophos, chromafenoside, cinerin I, cinerin II, cinerins, cismetrin, claciphos, cloetocarb, closantel, clothianidin, copper acetoarsenite, copper arsenate, naphtha copper enate, copper oleate , coumaphos, kumitoate, crotamiton, crotoxyphos, crufomat, cryolite, cyanofenphos, cyanophos, cyantoate, cyantraniliprole, cyclaniliprole, ciclethrin, cycloprothrin, cyfluthrin, cyhalothrin, cypermethrin, cyfenotrin, cyromazine, cythioate, DDT, decarbofuran, deltamethrin , demefion, demefion-O , demefion-S, demeton, demeton-methyl, demeton-O, demeton-O-methyl, demeton-S, demeton-S-methyl, demeton-S-methylsulfone, diafenthiuron, dialyphos, diatomaceous earth, diazinon, dicaptone, dichlofenthione, dichlorvos, dicloromesothiasis, dicresyl, dicrotophos, dicyclanil, dieldrin, diflubenzuron, dilor, dimefluthrin, dimefox, dimethane, dimethoate, dimethrin, dimethylvinphos, dimethylan, dinex, dinex-dikleksin, dinoprop, dinosam, dinotefuran, diofenolan, dioxabenzophos, dioxacarb , dioxation, Disphotone, dyticrophos, d-lemonone, dnoc, Dnoc-ammonium, Dnoc-kaliy, DNOC NATRY, PROMEMECTIN, ECTICTERON, EMAMEMECTIN, EMAMEMECTINE BAMPC, EMPC, Empants, Endosulfan, Endotion, EPN, EPOPHENONANE, EPOPHINE, EPONIMECTINE, EPONIMECTINE, EPONIMECTIN Palletin, Esfenvalerat , etaphos, ethiofencarb, ethion, ethiprole, etoate-methyl, etoprofos, ethyl formate, ethyl-DDD, ethylene dibromide, ethylene dichloride, ethylene oxide, etofenprox, etrymphos, EXD, famfur, fenamiphos, fenazaflor, fenchlorphos, fenetacarb, fenfluthrin, fenitrothion, fenobucarb, fenoxac rome , fenoxycarb, fenpyrythrin, fenpropatrin, fensulfothion, fenthion, fenthion-ethyl, fenvalerate, fipronil, flomethochine, flonikimid, flubendiamide, flucofuron, flucycloxuron, flucitrinate, flufenerim, flufenoxuron, flufenprox, flufiprol, fluhexafon, flupyradifuron , fluvalinate, fonofos, formetanate, formatenate hydrochloride, formotion, formparanate, formparanate hydrochloride, fosmethylan, fospirate, fostietane, furatiocarb, furethrin, gamma-cyhalothrin, gamma-HCH, galfenprox, halofenoside, HCH, HEOD, heptachlor, heptafluthrin, heptenophos, heterophos, hexaflumuron, HHDN, hydramethylnon, cyanide hydrogen, hydroprene, quiquincarb, imidacloprid, imiprotrin, indoxacarb, iodomethane, IPSP, isazophos, isobenzan, isocarbophos, isodrine, isofenphos, isofenphos-methyl, isoprocarb, isoprothiolan, isothioate, isoxathion, ivermectin, jasmolin I, jasmolin II, iodofenphos, juvenile hormone I, juvenile hormone II, juvenile hormone III, kappa-bifenthrin, kappa-tefluthrin, kelevan, kinoprene, lambda-cyhalothrin, lead arsenate, lepimectin, leptophos, lindane, lyrimphos, lufenuron, litidathione, malathion, malonoben, mazidox, mecarbam, mecarfon , menasone, mephospholane, mercuric chloride, mesulfenphos, metaflumizone, methacryphos, methamidophos, metidathione, methiocarb, methocrotophos, methomyl, methoprene, methoxychlor, methoxyfenoside, methyl bromide, methyl isothiocyanate, methyl chloroform, methylene chloride, metofluthrin, metolcarb, methox adiazon, mevinphos, mexacarbate, milbemectin, milbemycin oxime, mipafox, mirex, molosultap, momfluorothrin, monocrotophos, monomegipo, monosultap, morphothion, moxidectin, naftalofos, naled, naphthalene, nicotine, nifluridide, nitenpyram, nithiazine, nitrilacarb, novaluron, noviflumuron, ometoate, oxami l, oxydemeton-methyl, oxydeprofos , oxydisulfotone, para-dichlorobenzene, parathion, parathion-methyl, penfluron, pentachlorophenol, permethrin, phencaptone, phenothrin, phentoate, phorate, phosalone, phospholane, phosmet, fosnichlor, phosphamidon, phosphine, phoxim, phoxim-methyl, pyrimetaphos, pyrimicarb, pyrimiphos -ethyl, pyrimiphos-methyl, potassium arsenite, potassium thiocyanate, pp'-DDT, pralletrin, precocene I, precocene II, precocene III, primidophos, profenophos, profluralin, promacyl, promecarb, propafos, propetamphos, propoxur, protidathione, prothiophos, protoate , protrifenbut, piflubumide, pyraclophos, pyrafluprol, pyrazophos, pyresmethrin, pyrethrin I, pyrethrin II, pyrethrins, pyridaben, pyridalil, pyridafenthione, pyrifluquinasone, pyrimidifen, pyriminostrobin, pyrimitate, pyriprole, pyriproxyfen, quassia, quinalphos, quinalphos-methyl, quinothion, rafoxanide , Resmetrin, Rotenone, Ryanium, Sabadilla, Shradan, Selamectin, Silafluofen, Silica Gel, Sodium Arsenite, Sodium Fluoride, Sodium Hexafluorosilicate, Sodium Thiocyanate, Sofamide, Spinetoram, Spinosad, Spiromesifen, Spirotetramate, Sulcofuron, Sulcofuron Sodium, Sulfluramide, Sulfotep , sulfoxaflor , sulfuryl fluoride, sulprofos, tau-fluvalinate, tazimcarb, TDE, tebufenoside, tebufenpyrad, tebupyrimphos, teflubenzuron, tefluthrin, temephos, TEPP, teralletrin, terbufos, tetrachloroethane, tetrachlorvinphos, tetramethrin, tetramethylfluthrin, tetraniliprol, theta-cypermethrin, thiaclop reed, thiamethoxam, tikrofos , thiocarboxym, thiocyclam, thiocyclam oxalate, thiodicarb, thiofanox, thiometon, thiosultap, thiosultap-disodium, thiosultap-monosodium, thuringienzine, thioxazafen, tolfenpyrad, tralometrin, transfluthrin, transpermethrin, triaraten, triazamate, triazophos, trichlorfon, trichlormetaphos-3, trichloronate, tripenofos, triflumesopyrim, triflumuron, trimetacarb, triprene, vamidothione, vaniliprole, XMC, xylicarb, zetacypermethrin, zolaprofos, and any combination thereof.

[0042] Additionally, the compounds described herein can be combined with herbicides that are compatible with the compounds of the present disclosure in the medium chosen for use and are not antagonistic to the activity of these compounds to form pesticide mixtures and synergistic mixtures thereof. The fungicidal compounds of the present disclosure can be used in combination with one or more herbicides in order to control a wide range of unwanted plants. When used in combination 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, alorak, ametridion, ametrin, amibusin, amicarbazone, amidosulfuron, aminocyclopyrachlor, aminopyralid, amiprofos-methyl, amitrol, ammonium sulfamate, anilofos, anizuron, asulam, atraton, atrazine, azaphenidin, azimsulfuron, aciprothrin, barban, BCPC, beflubutamide, benazoline, bencarbazone, benfluralin, benfuresate, bensulfuron, bensulide, bentazone, benzadox, benzfendison, benzipram, benzobicyclone, benzofenap, benzofluor, benzoylprop, benzthiazuron, bicyclopyrone, bifenox, bilanafos, bispyribac, borax, bromacyl, bromobonyl, bromobutide, bromophenoxime, bromoxynil, bromopyrazone, butachlor, butafenacil, butamiphos, butenachlor, butidazole, buthiuron, butralin, butroxydim, buturon, butylate, cacodylic acid, cafenstrol, calcium chlorate, calcium cyanamide, cambendi chlorine, carbasulam , carbetamide, carboxazole, chlorprocarb, carfentrazone, CDEA, CEPC, chlormethoxifene, chloramben, chloranocryl, chlorazifop, chlorazine, chlorbromuron, chlorbufam, chlorethuron, chlorfenac, chlorfenprop, chlorflurazol, chlorflurenol, chloridazone, chlorimuron, chlornitrofen, chlorine opon, chlorotoluron, chloroxuron, chloroxynil , chlorpropham, chlorsulfuron, chlorthal, chlorthiamide, cynidone-ethyl, cinmethylin, cinosulfuron, cisanilide, clethodim, cliodinate, clodinafop, clofop, clomazone, clomeprop, cloprop, cloproxydim, clopyralid, cloransulam, CMA, copper sulfate, CPMF, CPPC, creda zine, cresol, cumiluron, cyanothrin, cyanazine, cycloate, cyclopyrimorate, cyclosulfamuron, cycloxidim, cycluron, cyhalofop, cyperquat, cyprazine, cyprazole, cypromide, daimuron, dalapon, dazomet, delachlor, desmedifam, desmetrin, diallat, dicamba, dichlobenil, dichloralurea, dichlor mat, Dichlorprop, Dichlorprop-P, Diclofop, Diclosulam, Dietamquat, Dietatyl, Diphenopentene, Difenoxuron, Difenzoquat, Diflufenican, Diflufenzopyr, Dimefuron, Dimepiperate, Dimethachlor, Dimethamethrin, Dimethenamid, Dimethenamid-P, Dimexano, Dimidazone, Dinitramine, Dinophenate, dinoprop, dinosam, dinoseb, dinoterb, diphenamide, dipropetrin, diquat, disul, dithiopyr, diuron, DMPA, DNOC, DSMA, EBEP, eglinazine, endothal, epronase, EPTC, erbon, esprocarb, ethalfluralin, ethametsulfuron, ethidimuron, etiolate, etofumesate, ethoxyphene, ethoxysulfuron, ethinophen, ethnipromide, etobenzanide, EXD, fenasulam, fenoprop, fenoxaprop, fenoxaprop-P, fenoxasulfone, fenquinotrion, fenteracol, fentiaprop, fentrazamide, fenuron, iron(II) sulfate, flamprop, flamprop-M, flazasulfuron, florasulam, fluazi fop, fluazifop- P, fluazolate, flucarbazone, flucetosulfuron, fluchloralin, flufenacet, flufenican, flufenpyr, flumetsulam, flumezin, flumiclorac, flumioxazine, flumipropine, fluometuron, fluorodifen, fluoroglycofen, fluoromidin, fluoronitrofen, fluothiuron, flupoxam, flu propacil, flupropanate, flupyrsulfuron, fluridone, flurochloridone, fluroxypyr, flurtamone, flutiacet, fomesafen, foramsulfuron, fosamine, furyloxifene, glufosinate, glufosinate-P, glyphosate, galauxifen, halosafen, halosulfuron, haloxydin, haloxyfop, haloxyfop-P, hexachloroacetone, hexaflurate, hexazinon, imazamethabenz, imazamox, imazapik, imazapir, imazaquin, imazethapir, imazosulfuron, indanophane, indaziflam, iodobonil, iodomethane, iodosulfuron, iofensulfuron, ioxynil, ipazine, ipfencarbazone, iprimidam, isocarbamide, isocyl, isomethiosin, isonoruron, isopolynate, isopropaline, isoproturon, isouron, isoxaben, isoxachlorotol, isox aflutol, isoxapyrifop, carbutilate, 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, metabenzthiazuron, metalpropalin, metazol, methiobencarb, methiozolin, methiuron, methomethone, metoprotrin, methyl bromide, methylisothiocyanate, methyldymron, methobenzuron, metobromuron, metolachlor, methosulam, methoxuron, metribuzin, metsulfuron, molinate, monalid, monisouron, monochloroacetic acid, monolinuron, monouron , morphamquat, MSMA, naproanilide, napropamide, napropamide-M, naptalam, neburon, nicosulfuron, nipyraclofen, nitralin, nitrofen, nitrofluorfen, norflurazon, noruron, OCH, orbencarb, ortho-dichlorobenzene, orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, oxapira zones, oxasulfuron , oxaziclomefon, oxyfluorfen, parafluron, paraquat, pebulate, pelargonic acid, pendimethalin, penoxulam, pentachlorophenol, pentanochlor, pentoxazone, perfluidone, petoxamide, fenizofam, phenmedifam, phenmedifam-ethyl, fenobenzuron, phenylmercury acetate, picloram, picolinafen, pinoxa den, piperophos, arsenite potassium, potassium azide, potassium cyanate, pretilachlor, primisulfuron, procyazine, prodiamine, profluazole, profluralin, profoxydim, proglinazine, promethone, promethrin, propachlor, propanil, propaquizafop, propazine, profam, propisochlor, propoxycarbazone, propyrisulfuron, propizamide, prosulfalin, prosulfocarb, Prosulfuron, Proxane, Prinachlor, Pidanone, Pyraclonil, Pyraflufen, Pyrasulfotol, Pyrazolinate, Pyrazosulfuron, Pyrazoxyfen, Pyribenoxime, Pyributicarb, Pyriclor, Pyridafol, Pyridate, Pyrifthalide, Pyriminobac, Pyrimisulfan, Pyrithiobac, Pyroxasulfone, Piroxulam, Quinclorac , quinmerac, quinoclamin, quinonamide, Quizalophop, Quizalophop-P, Rhodetnil, RimSusifuron, Saflufenacil, S-metolalor, Sebulazine, Sexton, Sedoxyim, Sudiron, Simazin, Simeton, Simetrin, SMA, Sodium Arsenitis, Sodium Azid, Sodium Chlorate, Sulfallat, Sulfentrazon, Sulfall. Meturon, sulfosulfuron , sulfuric acid, sulglycapine, swep, TCA, tebutam, tebuthiuron, tefuryltrione, tembotrione, tepraloxydim, terbacil, terbucarb, terbuchlor, terbumetone, terbutylazine, terbutrin, tetrafluron, tenylchlor, thiazafluron, thiazopyr, thidiazimin, thidiazuron, thiencarbazone-methyl , thifensulfuron, thiobencarb, thiafenacil, thiocarbazil, thioclorim, tolpyralate, topramesone, tralkosidim, triafamon, triallat, triasulfuron, triaziflam, tribenuron, tricamba, triclopyr, tridifan, trietazine, trifloxysulfuron, trifludimoxazine, trifluralin, triflusulfuron, trifop, trifops im, trihydroxytriazine, trimeturon, tripropindan, tritac, tritosulfuron, vernolate and xylachlor.

[0043] Another embodiment of the present disclosure is a method for controlling or preventing fungal infestation. This method comprises applying to the soil, plant, roots, foliage or site of the fungus, or to the site where infection is to be prevented (e.g., application to cereal plants or vine plants), a fungicidally effective amount of one or more compounds of formula I. The compounds are suitable for treatment of various plants at fungicidal levels, while exhibiting low phytotoxicity. The compounds can be used in both a protective and/or eradicative manner.

[0044] The compounds have been found to have a significant fungicidal effect, particularly for agricultural use. Many of the compounds are particularly effective for use with crops and fruit plants.

[0045] It will be appreciated by those skilled in the art that the effect of the compounds on the above fungi constitutes the primary utility of the compounds as fungicides.

[0046] The compounds have broad ranges of activity against fungal pathogens. Model pathogens may include, but are not limited to, the causative agent of wheat leaf spot (Zymoseptoria tritici), wheat leaf rust (Puccinia triticina), wheat yellow rust (Puccinia striiformis), apple scab (Venturia inaequalis), grapevine powdery mildew (Uncinula necator ), barley blight (Rhynchosporium secalis), rice blast (Pyricularia oryzae), soybean rust (Phakopsora pachyrhizi), wheat glume septoria (Leptosphaeria nodorum), wheat powdery mildew (Blumeria graminis f. sp. tritici), barley powdery mildew (Blumeria graminis f. sp. hordei), cucurbit powdery mildew (Erysiphe cichoracearum), cucurbit anthracnose (Colletotrichum lagenarium), beet leaf spot (Cercospora beticola), tomato alternaria blight (Alternaria solani) and barley helminthosporia blight (Cochliobolus sativus). The exact amount of active material to be applied depends not only on the particular active material applied, but also on the particular effect desired, the type of fungus to be controlled and its stage of growth, and the part of the plant or other product to be contacted with the compound. Thus, all compounds and formulations containing them may not be equally effective at similar concentrations or against the same fungal species.

[0047] The compounds are effective when used in plants in a disease-inhibitory and phytologically acceptable amount. The term "disease-inhibiting and phytologically acceptable amount" refers to an amount of a compound that kills or inhibits a plant disease for which control is desirable but is not significantly toxic to the plant. This amount is generally from about 0.1 to about 1000 ppm (parts per million), preferably from 1 to 500 ppm. The exact compound concentration required will vary with the fungal disease being controlled, the type of formulation used, application method, particular plant species, climatic conditions, and the like. A suitable application rate is typically in the range of about 0.10 to about 4 lb/acre ( approximately 0.01 to 0.45 grams per square meter, g/m ² ).

[0048] Any range or desired value set herein can be expanded or changed without losing the desired effects, as is obvious to a person skilled in the art to understand the provisions herein.

[0049] The compounds of formula I can be created using well-known chemical procedures. Intermediates not specifically mentioned in this disclosure are either commercially available or can be generated using routes disclosed in the chemical literature or can be readily synthesized from commercial starting materials using standard procedures.

GENERAL SCHEMES

[0050] The following schemes illustrate approaches to the design of formula I picolinamide compounds. The following descriptions and examples are provided for illustrative purposes and should not be construed as a limitation on substituents or patterns of substitution.

[0051] Compounds of Formula 1.1 wherein R ₃ and R ₁₂ are as originally defined and are equivalent can be prepared by the methods of Scheme 1, step a. A compound of formula 1.0 can be treated with an organometallic nucleophile such as phenylmagnesium bromide (PhMgBr) in a polar aprotic solvent such as tetrahydrofuran (THF) at a temperature of from about 0°C to 23°C to give compounds of formula 1.1 wherein R ₃ and R ₁₂ are as predetermined as shown in a.

Scheme 1

[0052] Compounds of formula 2.2 in which R ₃ is as predetermined and may or may not be equal to R ₁₂ can be prepared by the methods of scheme 2, step ac. Compounds of formula 2.2 in which R ₃ and R ₁₂ are as previously defined, but not an electron-deficient aryl or heteroaryl group, and may or may not be equivalent, can be prepared by treating compounds of formula 2.0 in which R ₃ and R ₁₂ is what is previously defined, but not an electron-deficient aryl or heteroaryl group, and may or may not be equivalent, using a mixture of a hydride reagent such as triethylsilane (Et ₃ SiH) and an acid such as 2,2, 2-trifluoroacetic acid (TFA), in a halogenated solvent such as dichloromethane (DCM), at a temperature of from about 0°C to 23°C, as shown in a. Alternatively, compounds of formula 2.1 in which R ₃ and R ₁₂ are an electron-deficient aryl or heteroaryl group and may or may not be equivalent can be prepared by treating compounds of formula 2.0 in which R ₃ and R ₁₂ are an electron-deficient aryl or heteroaryl group and may or may not be equivalent using a base such as sodium hydride (NaH) and a catalyst such as imidazole in a polar aprotic solvent such as THF at a temperature of approximately 23° C. followed by the sequential addition of carbon disulfide (CS ₂ ) and alkyl iodide such as iodomethane (MeI) as shown in b. Compounds of formula 2.2 in which R ₃ and R ₁₂ are an electron-deficient aryl or heteroaryl group and may or may not be equivalent can be prepared by treating compounds of formula 2.1 in which R ₃ and R ₁₂ are as previously defined, and may or may not be equivalent using a tin reagent such as tributyltin hydride and a radical initiator such as azobisisobutyronitrile (AIBN) in a nonpolar solvent such as toluene at a temperature of approximately 115°C as depicted in c.

Scheme 2

[0053] Compounds of formula 3.1 in which R ₃ and R ₁₂ are as originally defined and may or may not be equivalent can be prepared according to the method shown in Scheme 3, step a. Compounds of formula 3.1 in which R ₃ and R ₁₂ are as originally defined and may or may not be equivalent can be prepared from compounds of formula 3.0 in which R ₃ and R ₁₂ are as previously defined, and may or may not be equivalent by treatment with a base such as NaH and an alkyl halide such as MeI in a polar aprotic solvent such as N,N-dimethylformamide (DMF) at a temperature of from about 0° C. to 23° C. C as shown in a.

Scheme 3

[0054] Compounds of formula 4.1 in which R ₃ and R ₁₂ are as originally defined and may or may not be equivalent can be prepared according to the method shown in Scheme 4, step a. Compounds of formula 4.1 in which R ₃ and R ₁₂ are as originally defined and may or may not be equivalent can be prepared from compounds of formula 4.0 in which R ₃ and R ₁₂ are as previously defined, and may or may not be equivalent, by treatment with a fluorination reagent such as (diethylamino)sulfur trifluoride (DAST) in a halogenated solvent such as DCM at a temperature of approximately 0°C to 23°C as shown in a .

Scheme 4

[0055] Compounds of formula 5.3 in which R ₃ , R ₄ and R ₁₂ are as originally defined and R ₃ may or may not be equivalent to R ₁₂ can be prepared according to the methods shown in Scheme 5, stages ac. Compounds of formula 5.3 in which R ₃ , R ₄ and R ₁₂ are as originally defined and R ₃ may or may not be equivalent to R ₁₂ can be prepared from compounds of formula 5.0 in which R ₃ , R ₄ and R ₁₂ are as originally defined, and R ₃ may or may not be equivalent to R ₁₂ by treatment with a catalyst such as palladium on carbon (Pd/C) in a mixture of an unsaturated hydrocarbon solvent such as cyclohexene and a polar protic solvent such as ethanol (EtOH) at an elevated temperature of approximately 65°C as shown in a. Alternatively, compounds of formula 5.3 in which R ₃ and R ₁₂ are an electron-deficient aryl or heteroaryl group and may or may not be equivalent and R ₄ is hydroxyl (OH) or alkoxy can be prepared by treating compounds of formula 5.1 wherein R ₃ , R ₄ and R ₁₂ are as previously defined, and R ₃ may or may not be equivalent to R ₁₂ , a mixture of a hydride reagent such as Et ₃ SiH and an acid such as TFA in a halogenated solvent, such as DCM at approximately 0°C to 23°C as shown in b. Additionally, compounds of formula 5.3 in which R ₃ and R ₁₂ are as originally defined, but not an electron-deficient aryl or heteroaryl group, and may or may not be equivalent, and R ₄ is a proton (H), can be prepared by treating compounds of formula 5.2, in which R ₃ , R ₄ and R ₁₂ are as previously defined and R ₃ may or may not be equivalent to R ₁₂ , with a mixture of a hydride reagent such as Et ₃ SiH and an acid, such as TFA in a halogenated solvent such as DCM at a temperature of about 0°C to 23°C, as depicted in c.

Scheme 5

[0056] the Compounds of formula 6.2, in which R ₃ and R ₁₂ represent an electron-deficient aryl or heteroaryl group and the equivalent, can be obtained in accordance with the methods shown in scheme 6, stage ab. Compounds of formula 6.1 in which R ₃ and R ₁₂ are as previously described can be prepared from a compound of formula 6.0 by treatment with an aryl bromide such as 4-bromobenzonitrile in the presence of a Pd catalyst such as XPhos Pd G3 (CAS No. 1445085 -55-1, commercially available from Sigma-AldricH), in a polar aprotic solvent such as THF at approximately 55° C. as shown in a. Compounds of formula 6.2 in which R ₃ and R ₁₂ are as previously described can be prepared from a compound of formula 6.1 in which R ₃ and R ₁₂ are as previously described by treatment with a hydride reagent such as the borane dimethyl sulfide complex , in the presence of a catalyst such as (R)-(+)-2-methyl-CBS-oxazaborolidine in a polar protic solvent such as methanol (MeOH) at a temperature of approximately 0° C. as shown in b.

Scheme 6

[0057] Compounds of formula 7.2 wherein R ₃ and R ₁₂ are as originally defined and the equivalent can be prepared according to the methods shown in Scheme 7, step ab. Compounds of formula 7.1 in which R ₃ and R ₁₂ are as previously described can be prepared from compounds of formula 7.0 by treatment with a catalyst such as SbCl ₅ in a halogenated solvent such as DCM at a temperature of about 23°C, as shown in a. Compounds of formula 7.2 in which R ₃ and R ₁₂ are as previously described can be prepared from a compound of formula 7.1 in which R ₃ and R ₁₂ are as previously described by treatment with a hydride reagent such as a borane dimethyl sulfide complex , in the presence of a catalyst such as (R)-(+)-2-methyl-CBS-oxazaborolidine in a polar protic solvent such as methanol (MeOH) at a temperature of approximately 23° C. as shown in b.

Scheme 7

[0058] the Compounds of formula 8.1, in which n represents 0 or 1 and W represents CH ₂ or O, can be obtained in accordance with the method shown in scheme 8, stage a. Compounds of formula 8.1 in which n is 0 or 1 and W is CH ₂ or O can be prepared from compounds of formula 8.0 in which n is 0 or 1 and W is CH ₂ or O by treatment with a base such as as n-butyllithium (n-BuLi) and an aldehyde such as acetaldehyde in a polar aprotic solvent such as THF at a temperature of about -78°C to 23°C as shown in a.

Scheme 8

[0059] Compounds of formula 9.1, in which R ₃ and R ₁₂ represent what is originally defined, can be obtained in accordance with the method shown in scheme 9, stage a. Compounds of formula 9.1 in which R ₃ and R ₁₂ are as originally defined can be prepared from compounds of formula 9.0 in which R ₃ is as previously defined (formula 9.0 is either commercially available or can be prepared by asymmetric epoxidation of Shi corresponding E-olefin precursor, as reported in Wang, Z.-X.; Tu, Y.; Frohn, M; Zhang, J.-R.; Shi, YJ Am. Chem. Soc. 199711911224), by processing using a premixed suspension of a copper(I) salt such as copper iodide (CuI) and an organometallic nucleophile such as 4-(trifluoromethyl)phenylmagnesium bromide in a polar aprotic solvent such as THF at a temperature of about -78°C to 23 °C as shown in a.

schemes* 9

[0060] Compounds of formula 10.2 in which R ₁ , R ₂ , R ₃ , R ₄ and R ₁₂ are as originally defined can be prepared according to the method shown in Scheme 10, step a. Compounds of formula 10.0 in which R ₁ is as previously defined can be treated with alcohols of formula 10.1 in which R ₂ , R ₃ , R ₄ and R ₁₂ are as originally defined and a coupling agent such as 3 -(ethyliminomethyleneamino)-N,N-dimethylpropan-1-amine hydrochloride (EDC) and a catalyst such as N,N-dimethylpyridin-4-amine (DMAP) in a halogenated solvent such as DCM to give compounds of formula 10.2, in which R ₁ , R ₂ , R ₃ , R ₄ and R ₁₂ are as previously defined as shown in a.

Scheme 10

[0061] Compounds of formula 11.2 in which R ₁ , R ₂ , R ₃ , R ₄ , R ₆ , R ₁₂ and Z are as originally defined can be prepared according to the methods shown in Scheme 11, step ab . As shown in a, compounds of formula 11.2 in which R ₁ , R ₂ , R ₃ , R ₄ and R ₁₂ are as originally defined can be treated with an acid such as a 4 normal (H) hydrogen chloride solution ( HCl) in dioxane, in a halogenated solvent such as DCM to give compounds of formula 9.0 wherein R ₁ , R ₂ , R ₃ , R ₄ and R ₁₂ are as originally defined as shown in a.

[0062] Compounds of formula 11.0 in which R ₁ , R ₂ , R ₃ , R ₄ and R ₁₂ are as originally defined can be treated with compounds of formula 11.1 in which R ₆ and Z are as originally defined , in the presence of a base such as diisopropylethylamine (DIPEA) and a peptide coupling reagent such as benzotriazol-1-yl-oxytripyrrolidinophosphonium hexafluorophosphate (PyBOP) in a halogenated solvent such as DCM to give compounds of formula 11.2 in which R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₁₂ and Z are as originally defined as shown in b.

Scheme 11

[0063] Compounds of Formula 12.0 wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₆ , R ₇ , R ₁₂ and Z are as originally defined can be prepared according to the method shown in Scheme 12 , stage a. As shown in a, compounds of formula 11.2 in which R ₁ , R ₂ , R ₃ , R ₄ , R ₆ , R ₁₂ and Z are as originally defined can be treated with a suitable alkyl halide with or without the use of a reagent such as as sodium iodide (NaI) and an alkali carbonate base such as sodium carbonate (Na ₂ CO ₃ ) or potassium carbonate (K ₂ CO ₃ ) in a solvent such as acetone at a temperature of about 55°C, or by treatment with an acyl halide in the presence of an amine base, such as pyridine, triethylamine (Et ₃ N), DMAP, or mixtures thereof, in an aprotic solvent, such as DCM, at a temperature of approximately 23°C, in order to obtain compounds of formula 12.0, in which R ₁ , R ₂ , R ₃ , R ₄ , R ₆ , R ₇ , R ₁₂ and Z are as originally defined.

Scheme 12

EXAMPLES

[0050] The chemical reactions in the following examples can be carried out using the enantiomer of 2-((tert-butoxycarbonyl)amino)propanoic acid (Boc-Ala-OH) or any of the protected (PMB or Bn) or unprotected ethyl lactate enantiomer.

[0051] Example 1: preparation of (S)-2-(benzyloxy)-1,1-bis(4-fluorophenyl)propan-1-ol.

[0052] To a solution of (S)-ethyl 2-(benzyloxy)propanoate (2.08 grams (g), 10.0 millimoles (mmol)) in tetrahydrofuran (THF; 20 milliliters (ml)) at 0°C was slowly added (4-fluorophenyl) magnesium bromide (31.3 ml, 25.0 mmol, 0.8 molar (M) in THF) over a period of 10 minutes (min). The reaction vessel was allowed to slowly warm to room temperature over 2 hours (h) and the reaction mixture was quenched by careful addition of saturated (sat.) aqueous (aq.) ammonium chloride (NH ₄ Cl; 50 ml). The mixture was diluted with diethyl ether (Et ₂ O; 50 ml), the phases were separated, and extracted with aq. phase using Et ₂ O (2×50 ml). The combined organic phases were washed with sat. aq. sodium chloride (NaCl, brine; 100 ml), dried over sodium sulfate (Na ₂ SO ₄ ), filtered and concentrated. The resulting oil was purified by flash column chromatography (silica gel (SiO ₂ ), 0->5% acetone in hexanes) to give the title compound (3.28 g, 93%) as a colorless oil: ¹ H NMR (300 MHz, CDCl ₃ ) δ 7.47-7.38 (m, 2H), 7.38-7.27 (m, 5H), 7.17-7.09 (m, 2H), 7.04 -6.89 (m, 4H), 4.64 (dd, J=11.4, 0.7 Hz, 1H), 4.51-4.38 (m, 2H), 3.12 (s, 1H ), 1.11 (d, J=6.1 Hz, 3H); ¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -116.19, -116.41; ESFMS m/z 377 ([M+Na] ⁺ ).

[0053] Example 2A: Preparation of (S)-4,4'-(2-(benzyloxy)propane-1,1-diyl)bis(fluorobenzene).

[0054] To a solution of (S)-2-(benzyloxy)-1,1-bis(4-fluorophenyl)propan-1-ol (709 milligrams (mg), 2.00 mmol) in dichloromethane (DCM; 20 mL) triethylsilane (Et ₃ SiH; 3.19 ml, 20.0 mmol) was added at 0° C. followed by 2,2,2-trifluoroacetic acid (TFA; 1.53 ml, 20.0 mmol). The mixture was stirred at 0° C. for 1 hour. The resulting solution was quenched by careful addition of sat. aq. sodium bicarbonate (NaHCO ₃ ; 20 ml). The phases were separated and extracted with aq. phase using DCM (2×30 ml). The combined organic phases were washed with brine (50 ml), dried over Na ₂ SO ₄ , filtered and concentrated. The resulting oil was purified by flash column chromatography (SiO ₂ , 0->10% acetone in hexanes) to give the title compound (627 mg, 92%) as a white solid: ¹ H NMR (400 MHz , CDCl ₃ ) δ 7.31-7.22 (m, 5H), 7.21-7.16 (m, 2H), 7.10-7.03 (m, 2H), 7.00-6, 91 (m, 4H), 4.54 (dd, J=11.5, 0.7 Hz, 1H), 4.31 (dd, J=11.6, 0.8 Hz, 1H), 4.14 (dc, J=8.1, 6.1 Hz, 1H), 3.93 (d, J=8.1 Hz, 1H), 1.18 (d, J=6.0 Hz, 3H); ¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -116.60, -117.10; ESFMS (m/z) 361 ([M+Na] ⁺ ).

[0055] Example 1B: preparation of (S)-(2-(benzyloxy)-1-methoxypropan-1,1-diyl)dibenzene.

[0056] To a suspension of sodium hydride (NaH; 52.0 mg, 1.30 mmol, 60% w/w (w/w) in mineral oil) in N,N-dimethylformamide (DMF; 3 ml) at 0°C was added a solution of (S)-2-(benzyloxy)-1,1-diphenylpropan-1-ol (318 mg, 1 mmol) in DMF (1 ml). The reaction mixture was stirred at room temperature for 30 min and then cooled to 0°C. Iodomethane (MeI; 93.0 microliters (µl), 1.50 mmol) was added and the reaction mixture was stirred at room temperature for 1 hour. The resulting solution was quenched by carefully adding sat. aq. NaHCO ₃ (10 ml). The mixture was diluted with diethyl ether (Et ₂ O; 10 ml), the phases were separated and extracted with aq. phase using Et ₂ O (2×10 ml). The combined organic phases were washed with brine (20 ml), dried over Na ₂ SO ₄ , filtered and concentrated. The resulting oil was purified by flash column chromatography (SiO ₂ , 0->5% acetone in hexanes) to give the title compound (295 mg, 89%) as a colorless oil: ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.47-7.41 (m, 2H), 7.40-7.35 (m, 2H), 7.33-7.18 (m, 11H), 4.69 (d, J= 11.9 Hz, 1H), 4.54 (d, J=12.3 Hz, 1H), 4.50 (c, J=6.1 Hz, 1H), 3.13 (s, 3H), 1 .10 (d, J=6.1 Hz, 3H); ¹³ C NMR (101 MHz, CDCl ₃ ) δ 142.96, 141.31, 138.79, 129.13, 128.54, 128.14, 127.61, 127.16, 127.08, 126.95 , 126.69, 99.99, 85.35, 78.13, 70.80, 52.46, 13.65; ESFMS (m/z) 333 ([M+H] ⁺ ).

[0057] Example 2C: Preparation of (S)-(2-(benzyloxy)-1-fluoropropane-1,1-diyl)dibenzene.

[0058] To a solution of (S)-2-(benzyloxy)-1,1-diphenylpropan-1-ol (300 mg, 0.942 mmol) in DCM (5 ml) at 0°C was added (diethylamino)sulfur trifluoride (DAST; 1.88 ml, 1.88 mmol, 1 M in DCM). The reaction was slowly warmed to room temperature over 3 hours. The resulting solution was quenched by careful addition of sat. aq. NaHCO ₃ (5 ml). The phases were separated and extracted with aq. phase using DCM (2×10 ml). The combined organic phases were washed with brine (10 ml), dried over Na ₂ SO ₄ , filtered and concentrated. The resulting oil was purified by flash column chromatography (SiO ₂ , 0->10% acetone in hexanes) to give the title compound (300 mg, 98%) as a colorless oil: ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.58-7.49 (m, 2H), 7.43-7.37 (m, 2H), 7.36-7.20 (m, 9H), 7.09-6.99 ( m, 2H), 4.47 (d, J=11.7 Hz, 1H), 4.37-4.25 (m, 2H), 1.26 (dd, J=6.3, 1.3 Hz , 3H); ¹³ C NMR (101 MHz, CDCl ₃ ) δ 142.23 (d, J=22.7 Hz), 141.00 (d, J=23.5 Hz), 138.03, 128.21, 128.16 , 127.90 (d, J=1.5 Hz), 127.80, 127.72 (d, J=1.7 Hz), 127.52, 127.42 (d, J=1.3 Hz) , 126.23 (d, J=9.6 Hz), 125.93 (d, J=8.7 Hz), 99.96 (d, J=180.8 Hz), 78.91 (d, J =26.9 Hz), 71.68, 14.47 (d, J=3.6 Hz); ¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -159.80.

[0059] Example 2D, Step 1: Preparation of (S)-O-(2-(benzyloxy)-1,1-bis(3,4,5-trifluorophenyl)propyl) S-methylcarbonodithioate.

[0060] To a solution of (S)-2-(benzyloxy)-1,1-bis(3,4,5-trifluorophenyl)propan-1-ol (496 mg, 1.16 mmol) in anhydrous THF (5.8 mL) NaH (93.0 mg, 2.33 mmol) was added followed by imidazole (3.96 mg, 0.0580 mmol) and the reaction mixture was stirred at ambient temperature for 1 h. Carbon disulfide (562 μL, 9 .30 mmol) was added via syringe in one part followed by MeI (579 μl, 9.30 mmol) and the reaction mixture was stirred at ambient temperature for 2 h. The reaction mixture was diluted in Et ₂ O (5 ml) and quenched with using sat. aq. NH ₄ Cl (10 ml). The layers were separated and aq. the layer was extracted using Et ₂ O (3×10 ml). The combined organic layers were dried over magnesium sulfate (MgSO ₄ ), filtered and concentrated to give an orange/brown oil. The crude oil was purified by flash column chromatography (SiO ₂ , 0->50% ethyl acetate (EtOAc) in hexanes) to give the title compound (627 mg, 94%) as a light yellow clear oil: ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.40-7.27 (m, 3H), 7.24-7.16 (m, 2H), 7.02 (dd, J=9.1.6 .6 Hz, 2H), 6.96 (dd, J=8.8, 6.5 Hz, 2H), 5.44 (c, J=6.1 Hz, 1H), 4.66 (d, J =11.6 Hz, 1H), 4.51 (d, J=11.6 Hz, 1H), 2.49 (s, 3H), 1.16 (d, J=6.1 Hz, 3H); ¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -133.89 (d, J=20.7 Hz), -134.73 (d, J=20.6 Hz), -159.83 (t, J= 20.6 Hz), -160.56 (t, J=20.7 Hz); (Thin Film) 2922, 1721, 1622, 1595, 1526, 1436, 1344, 1241, 1217, 1197, 1119, 1088, 1040, 965, 908, 861, 822, 730, 712, 697, 6 72 cm ^-1 .

[0061] Example 2D, Step 2: Preparation of (S)-5,5'-(2-(benzyloxy)propane-1,1-diyl)bis(1,2,3-trifluorobenzene).

[0062] A solution of (S)-O-(2-(benzyloxy)-1,1-bis(3,4,5-trifluorophenyl)propyl) S-methylcarbonodithioate (598 mg, 1.16 mmol) in toluene (200 ml ) was degassed by a freeze-pump-thaw procedure (3 cycles using liquid nitrogen (N ₂ )) under N ₂ atmosphere. Tributylol hydride (3.12 mL, 11.6 mmol) was then added, the reaction flask was connected to a countercurrent condenser, and the reaction mixture was heated to slight reflux (115°C). A solution of azobisisobutyronitrile (AIBN; 0.200 g, 1.22 mmol) in degassed toluene (3 cycles through liquid N ₂ ; 32 mL) was added via syringe down the condenser with countercurrent over 3 h. refrigerator during the night. The solvent was removed in vacuo to give a pale yellow oil. The crude oil was purified by flash column chromatography (SiO ₂ , 0->30% EtOAc in hexanes) to give the title compound (358 mg, 72%) as a clear colorless oil: ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.28 (d, J=6.6 Hz, 3H), 7.17-7.06 (m, 2H), 6.92 (dd, J=8.5, 6.5 Hz, 2H), 6.79 (dd, J=8.3, 6.4 Hz, 2H), 4.59 (d, J=11.7 Hz, 1H), 4.31 (d, J=11.7 Hz, 1H), 4.02 (p, J=6.2 Hz, 1H), 3.76 (d, J=6.8 Hz, 1H), 1.19 (d, J=6.1 Hz, 3H); ¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -133.80 (d, J=20.5 Hz), -134.34 (d, J=20.5 Hz), -162.54 (t, J= 20.5 Hz), -162.84 (t, J=20.5 Hz); (Thin film) 2871, 1621, 1526, 1445, 1345, 1262, 1235, 1116, 1096, 1043, 859, 802, 728, 698, 679 cm ^-1 .

[0063] Example 3A: preparation of (S)-1,1-bis(4-fluorophenyl)propan-2-ol.

[0064] To a solution of (S)-4,4'-(2-(benzyloxy)propan-1,1-diyl)bis(fluorobenzene) (575 mg, 1.70 mmol) in ethanol (EtOH; 11 mL) and cyclohexene (5.5 ml) at room temperature was added palladium on carbon (Pd/C; 362 mg, 0.0850 mmol, 2.5% w/w Pd). The reaction mixture was stirred at 65° C. for 2 h, cooled to room temperature, filtered through a Celite® stopper and concentrated to give the title compound (415 mg, 98%) as a colorless oil: ¹ H NMR ( 400 MHz, CDCl ₃ ) δ 7.36-7.29 (m, 2H), 7.25-7.18 (m, 2H), 7.09-6.93 (m, 4H), 4.47 ( dcd, J=8.2, 6.1, 3.3 Hz, 1H), 3.80 (d, J=8.3 Hz, 1H), 1.55 (d, J=3.3 Hz, 1H ), 1.19 (d, J=6.1 Hz, 3H); ¹³ C NMR (101 MHz, CDCl ₃ ) δ 162.90 (d, J=23.3 Hz), 160.46 (d, J=23.1 Hz), 138.15 (d, J=3.1 Hz), 136.94 (d, J=3.6 Hz), 130.14 (d, J=7.8 Hz), 129.55 (d, J=7.8 Hz), 115.70 (d , J=18.8 Hz), 115.49 (d, J=18.8 Hz), 70.07, 58.61, 21.63; ¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -115.84, -116.19.

[0065] Example 3B: preparation of (S)-1,1-bis(2-fluorophenyl)propane-1,2-diol.

[0066] To a solution of (S)-1,1-bis(2-fluorophenyl)-2-((4-methoxybenzyl)oxy)propan-1-ol (790 mg, 2.06 mmol) in DCM (20 mL) at 0° C., Et ₃ SiH (3.28 ml, 20.6 mmol) was added followed by TFA (1.57 ml, 20.6 mmol). The mixture was stirred at 0° C. for 1 hour. The resulting solution was quenched by careful addition of sat. aq. NaHCO ₃ (20 ml). The phases were separated and extracted with aq. phase using DCM (2×30 ml). The combined organic phases were washed with brine (50 ml), dried over Na ₂ SO ₄ , filtered and concentrated. The resulting oil was purified by flash column chromatography (SiO ₂ , 0->10% acetone in hexanes) to give the title compound (388 mg, 71%) as a colorless oil: ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.90-7.77 (m, 1H), 7.70 (tt, J=8.2, 1.5 Hz, 1H), 7.31-7.10 (m, 4H), 6 .97 (ddd, J=12.7, 8.1, 1.3 Hz, 1H), 6.88 (ddd, J=11.8, 8.0, 1.4 Hz, 1H), 5.11 (cd, J=6.3, 2.3 Hz, 1H), 3.49 (s, 1H), 2.27 (s, 1H), 1.09 (d, J=6.3 Hz, 3H) ; ¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -112.90 (d, J=8.3 Hz), -113.92 (d, J=8.4 Hz); ESIMS (m/z) 551 ([2M+Na] ⁺ ).

[0067] Example 3C: preparation of (S)-1,1-bis(4-bromophenyl)propan-2-ol.

[0068] To a solution of (S)-1,1-bis(4-bromophenyl)-2-((4-methoxybenzyl)oxy)propan-1-ol (1.80 g, 3.56 mmol) in DCM (18 ml) at 0°C was added Et ₃ SiH (5.68 ml, 35.6 mmol), followed by TFA (2.72 ml, 35.6 mmol). The mixture was warmed slowly to room temperature over 3 hours. The resulting solution was quenched by careful addition of sat. aq. NaHCO ₃ (20 ml). The phases were separated and extracted with aq. phase using DCM (2×30 ml). The combined organic phases were washed with brine (50 ml), dried over Na ₂ SO ₄ , filtered and concentrated. The resulting oil was purified by flash column chromatography (SiO ₂ , 0->10% acetone in hexanes) to give the title compound (742 mg, 56%) as a colorless oil: ¹ H NMR (300 MHz, CDCl ₃ ) δ 7.51-7.36 (m, 4H), 7.25-7.17 (m, 2H), 7.18-7.06 (m, 2H), 4.48 (dc, J= 8.2, 6.1 Hz, 1H), 3.76 (d, J=8.2 Hz, 1H), 2.80 (s, 1H), 1.19 (d, J=6.2 Hz, 3H); ¹³ C NMR (75 MHz, CDCl ₃ ) δ 140.94, 139.85, 131.98, 131.85, 130.39, 129.84, 121.06, 120.72, 69.82, 58.91 , 21.65; (Thin film) 3390, 3024, 2969, 2900, 1486, 1072 cm ^-1 .

[0069] Example 3D, Step 1: Preparation of (S)-1,1-bis(4-((trimethylsilyl)ethynyl)phenyl)propan-2-ol.

[0070] Bis(triphenylphosphine)palladium dichloride (0.095 g, 0.136 mmol) and copper(I) iodide (CuI; 0.026 g, 0.136 mmol). The mixture was sparged with N ₂ for 20 min and triethylamine (Et ₃ N; 4.53 ml) was added dropwise. Ethynyltrimethylsilane (1.15 mL, 8.15 mmol) was added dropwise to the resulting mixture, and the mixture was heated to reflux and stirred overnight. The mixture was cooled to room temperature and the reaction was quenched using sat. aq. _NaHC03 . The products were extracted with EtOAc (2x) and the combined organic layers were washed with brine, dried over Na ₂ SO ₄ , filtered and concentrated. The crude residue was then purified by flash column chromatography (SiO ₂ , 0->20% acetone in hexanes) to give the title compound (495 mg, 45%) as a brown foam: ¹ H NMR (400 MHz , CDCl ₃ ) δ 7.48-7.42 (m, 2H), 7.42-7.37 (m, 2H), 7.33-7.27 (m, 2H), 7.24-7, 17 (m, 2H), 4.51 (dcd, J=12.2, 6.1, 3.5 Hz, 1H), 3.81 (d, J=8.3 Hz, 1H), 1.60 (d, J=3.8 Hz, 1H), 1.18 (d, J=6.1 Hz, 3H), 0.26 (s, 9H), 0.26 (s, 9H); ¹³ C NMR (101 MHz, CDCl ₃ ) δ 142.55, 141.48, 132.42, 132.29, 128.69, 128.15, 121.90, 121.57, 104.76, 104.71 , 94.49, 94.33, 69.76, 59.96, 21.55, 0.00; (Thin film) 3397, 2960, 2156, 1501, 1248, 861, 840 cm ^-1 ; HRMS-ESI (m/z) [M+H] ⁺ calculated for C ₂₅ H ₃₃ OSi ₂ , 405.2064; found 405,2070.

[0071] Example 3D, Step 2: Preparation of (S)-1,1-bis(4-ethynylphenyl)propan-2-ol.

[0072] To a solution of (S)-1,1-bis(4-((trimethylsilyl)ethynyl)phenyl)propan-2-ol (0.470 g, 1.16 mmol) in methanol (MeOH; 5.8 mL) was added potassium carbonate (K ₂ CO ₃ ; 0.482 g, 3.48 mmol). The mixture was stirred for 1 hour at room temperature and then filtered through Celite®. The filter cake was washed with MeOH and the filtrate was concentrated. The crude material was purified by flash column chromatography (SiO ₂ , 0->20% acetone in hexanes) to give the title compound (288 mg, 95%) as a yellow oil: ¹ H NMR (300 MHz, CDCl ₃ ) δ 7.48-7.43 (m, 2H), 7.43-7.39 (m, 2H), 7.35-7.29 (m, 2H), 7.24-7.19 (m, 2H), 4.51 (dcd, J=8.3, 6.1, 3.7 Hz, 1H), 3.82 (d, J=8.3 Hz, 1H), 3.05 ( s, 1H), 3.04 (s, 1H), 1.63-1.55 (m, 1H), 1.18 (d, J=6.1 Hz, 3H); ¹³ C NMR (101 MHz, CDCl ₃ ) δ 142.84, 141.82, 132.60, 132.48, 128.74, 128.22, 120.87, 120.57, 83.31, 83.29 , 77.39, 77.29, 69.73, 59.96, 21.66; (Thin film) 3436, 3280, 2968, 2106, 1499, 1075, 825 cm ^-1 ; HRMS-ESI (m/z) [M+H] ⁺ calculated for C ₁₉ H ₁₇ O, 261.1274; found 261,1272.

[0073] Example 3D, Step 3: Preparation of (S)-1,1-bis(4-ethylphenyl)propan-2-ol.

[0074] Palladium (5% by weight (wt.) on carbon, dry weight; 0.235 g, 0.055 mmol). The mixture was stirred under hydrogen atmosphere overnight. The mixture was filtered through Celite® and the filter cake was washed in EtOAc. The combined filtrate was then concentrated and the crude residue was purified by flash column chromatography (SiO ₂ , 0->25% acetone in hexanes) to give the title compound (97.0 mg, 65%) as a clear oil: ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.33-7.25 (m, 2H), 7.22-7.15 (m, 2H), 7.18-7.11 (m, 2H), 7 .10 (d, J=8.1 Hz, 2H), 4.51 (dcd, J=8.7, 6.1, 2.5 Hz, 1H), 3.74 (d, J=8.9 Hz, 1H), 2.65-2.53 (m, 4H), 1.68 (d, J=2.8 Hz, 1H), 1.23-1.14 (m, 9H); ¹³ C NMR (101 MHz, CDCl ₃ ) δ 142.74, 142.33, 139.94, 138.91, 128.48, 128.40, 128.07, 128.02, 70.19, 60.02 , 28.41, 28.39, 21.37, 15.47, 15.46; (Thin film) 3421, 2963, 1510, 1110, 821 cm ^-1 ; HRMS-ESI (m/z) ([M+Na] ⁺ ) calculated for C ₁₉ H ₂₄ NaO, 291.1719; found 291.1725.

[0075] Example 3E: preparation of 1-(9H-xanthen-9-yl)ethanol.

[0076] To a solution of 9H-xanthene (364 mg, 2.00 mmol) in THF (10 ml) at -78°C was added n-butyllithium (2.5 M in hexanes; 0.880 ml, 2.20 mmol). The mixture was stirred at -78°C for 30 minutes. Acetaldehyde (0.226 ml, 4.00 mmol) was added and the reaction mixture was heated slowly to room temperature overnight. The resulting solution was quenched by careful addition of sat. aq. NH ₄ Cl (10 ml). The phases were separated and extracted with aq. phase using Et ₂ O (2×15 ml). The combined organic phases were washed with brine (20 ml), dried over Na ₂ SO ₄ , filtered and concentrated. The resulting oil was purified by flash column chromatography (SiO ₂ , 0->10% acetone in hexanes) to give the title compound (216 mg, 48%) as a colorless oil: ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.33-7.22 (m, 4H), 7.17-7.04 (m, 4H), 3.99 (d, J=5.1 Hz, 1H), 3.96-3 .82 (m, 1H), 1.54 (d, J=6.0 Hz, 1H), 1.00 (d, J=6.3 Hz, 3H); ¹³ C NMR (101 MHz, CDCl ₃ ) δ 152.94, 152.65, 129.54, 129.30, 128.19, 128.17, 123.18, 123.14, 122.48, 121.73 , 116.59, 116.41, 73.07, 47.06, 18.81; ESFMS (m/z) 475 ([2M+Na] ⁺ ).

[0077] Example 3F: preparation of (1S,2S)-1-phenyl-1-(4-(trifluoromethyl)phenyl)propan-2-ol.

[0078] To a mixture of magnesium turnings (102 mg, 4.20 mmol) in Et ₂ O (4 ml) was added 1-bromo-4-(trifluoromethyl)benzene (0.588 ml, 4.20 mmol) at room temperature, after which followed by MeI (5 μl). After heating to a light boil using a heat gun, the mixture turned yellow/brown. The reaction was then stirred in a water bath at room temperature for 30 minutes until nearly all of the magnesium had been consumed. This was added to a suspension of copper (I) iodide (CuI; 400 mg, 2.10 mmol) in Et ₂ O (4 ml) at -78°C. The reaction was stirred at -20°C for 30 min, then cooled to -78°C and (2,S,3S)-2-methyl-3-phenyloxirane (0.201 ml, 1.50 mmol) was added. The resulting mixture was slowly warmed to room temperature overnight. The resulting solution was quenched by careful addition of sat. aq. NH ₄ Cl (10 ml). The phases were separated and extracted with aq. phase using Et ₂ O (2×15 ml). The combined organic phases were washed with brine (20 ml), dried over Na ₂ SO ₄ , filtered and concentrated. The resulting oil was purified by flash column chromatography (SiO ₂ , 0->10% acetone in hexanes) to give the title compound (390 mg, 94%) as a light yellow oil: ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.60-7.50 (m, 2H), 7.48-7.38 (m, 2H), 7.38-7.33 (m, 4H), 7.30-7 .23 (m, 1H), 4.58 (dcd, J=8.4, 6.1, 3.5 Hz, 1H), 3.88 (d, J=8.5 Hz, 1H), 1, 65 (d, J=3.6 Hz, 1H), 1.20 (d, J=6.1 Hz, 3H); ¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -62.49; ESFMS (m/z) 263 ([M-OH] ⁺ ).

[0079] Example 3G, Step 1: Preparation of 4,4'-(2-oxopropan-1,1-diyl)dibenzonitrile.

[0080] Acetone ( _1.10 ml, 15.00 mmol) followed by X-Phos Pd G3 (50.8 mg, 0.060 mmol). The suction was then sealed and heated to 55° C. for 4 days. The reaction was diluted with EtOAc (30 ml) and washed with sat. NH ₄ Cl (3×10 ml), water (15 ml) and saline (15 ml). The organic phase was then dried over Na ₂ SO ₄ , filtered and concentrated. The resulting oil was purified by flash column chromatography (SiO ₂ , 0->40% EtOAc in hexanes) to give the title compound (174 mg, 22%) as a colorless oil: ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.66 (d, J=8.4 Hz, 4H), 7.34 (d, J=8.3 Hz, 4H), 5.21 (s, 1H), 2.29 (s, 3H); ¹³ C NMR (101 MHz, CDCl ₃ ) δ 203.68, 142.15, 132.75, 129.64, 118.21, 112.00, 64.25, 30.43; ESFMS m/z 261 ([M+H] ⁺ ).

[0081] Example 3G, Step 2: Preparation of (S)-4,4'-(2-hydroxypropan-1,1-diyl)dibenzonitrile.

[0082] (R)-1-methyl-3,3- diphenylhexahydropyrrolo[1,2-c][1,3,2]oxazaborole (1 M solution in toluene, 66.8 µl, 0.067 mmol). The reaction was then cooled to 0° C. and a solution of BH ₃ -DMS (69.8 μl, 0.735 mmol) in 0.5 ml toluene was added over 2 minutes. The flask was left to stir at 0°C. After 2 hours the reaction was quenched with methanol (0.5 ml), diluted with EtOAc and water added. The phases were separated and the aqueous phase was extracted using EtOAc ×2. The combined organic phases were washed with brine (20 ml), dried over Na ₂ SO ₄ , filtered and concentrated. The resulting oil was purified by flash column chromatography (SiO ₂ , 0->50% EtOAc in hexanes) to give the title compound (99.7 mg, 57%) as a colorless oil: ¹ H NMR (400 MHz , CDCl ₃ ) δ d 7.60 (dd, J=8.4, 6.8 Hz, 4H), 7.51-7.46 (m, 2H), 7.43-7.37 (m, 2H ), 4.63-4.47 (m, 1H), 3.97 (d, J=7.5 Hz, 1H), 1.97 (d, J=3.8 Hz, 1H), 1.21 (d, J=6.2 Hz, 3H). ¹³ C NMR (101 MHz, CDCl ₃ ) δ 146.91, 145.86, 132.60, 132.45, 129.90, 129.19, 118.58, 118.51, 110.96, 110.92 , 69.19, 59.56, 22.27; ESFMS m/z 263 ([M+H] ⁺ ).

[0083] Example 3H, Step 1: Preparation of 3,3-diphenylbutan-2-one.

[0084] To a magnetically stirred mixture of 2,3-diphenylbutane-2,3-diol (500 mg, 2.06 mmol) in DCM (10 ml) was added antimony pentachloride (26.5 μl, 0.206 mmol) in air atmosphere. The reaction mixture was stirred at 25° C. for 1 h and then quenched by slowly adding sat. aq. _NaHC03 . The resulting mixture was diluted with water and additional DCM and the organic layer was separated by passing through a phase separator. The resulting oil was purified by flash column chromatography (SiO ₂ , 0->5% acetone in hexanes) to give the title compound (330 mg, 71%) as a colorless oil: ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.36-7.31 (m, 4H), 7.30-7.25 (m, 2H), 7.23-7.15 (m, 4H), 2.11 (s, 3H) , 1.87 (s, 3H); ¹³ C NMR (101 MHz, CDCl ₃ ) δ 209.16, 143.59, 128.36, 126.91, 62.32, 27.62, 26.42; ESFMS m/z225 ([M+H] ⁺ ).

[0085] Example 3H, Step 2: Preparation of (S)-3,3-diphenylbutan-2-ol.

[0086] To a solution of 3,3-diphenylbutan-2-one (150 mg, 0.669 mmol) in toluene (4.5 mL) was added (R)-1-methyl-3,3-diphenylhexahydropyrrolo[1,2-c] [1,3,2]oxazaborole (1 M solution in toluene, 134 µl, 0.134 mmol). Then a solution of BH ₃ -DMS (70.2 μl, 0.702 mmol) in 0.5 ml of toluene was added to the reaction mixture over 2 minutes. The flask was allowed to stir at room temperature. After 1 h the reaction was quenched with methanol (0.5 ml). DCM and water were added and the phases were separated. The aqueous phase was extracted using DCM (2×). The combined organic phases were washed with brine (20 ml), dried over Na ₂ SO ₄ , filtered and concentrated. The resulting oil was purified by flash column chromatography (SiO ₂ , 0->20% acetone in hexanes) to give the title compound (150 mg, 99%) as a colorless oil: ¹ H NMR (400 MHz, CDCl ₃ ) δ d 7.39-7.17(m, 10H), 4.70-4.61(m, 1H), 1.67(s, 3H), 1.51(d, J=4.9 Hz, 1H), 1.11 (d, J=6.3 Hz, 3H); ¹³ C NMR (101 MHz, CDCl ₃ ) δ 147.30, 145.86, 128.40, 128.15, 128.05, 127.79, 126.20, 126.01, 72.28, 51.77 , 23.26, 18.39; ESFMS m/z 227 ([M+H] ⁺ ).

[0087] Example 31, Step 1: Preparation of (S)-1,1-bis(2,3-dimethoxyphenyl)propane-1,2-diol.

[0088] To a solution of lithium isopropylmagnesium chloride (1.3 M in THF, 6.1 mL, 8.00 mmol) was added THF (2 mL) and 1-bromo-2,3-dimethoxybenzene (1.74 g, 8.00 mmol). 00 mmol). The resulting brown solution was heated to a slight reflux (external temperature 75° C.) for 2.5 I, then cooled to 0° C. in an ice water bath. Then (S)-methyl 2-hydroxypropanoate (0.191 mL, 2 mmol) was added dropwise via syringe. The reaction was stirred at 0°C for 1 h, then removed from the cold bath and stirred over night at it. The reaction was cooled to 0° C. in an ice water bath, diluted with water (20 ml), brine (20 ml) and Et ₂ O (40 ml) and quenched using 1 N HCl (8 ml). The phases were separated and the aqueous phase was extracted with Et ₂ O (20 ml). The organic phases were combined, dried over MgSO ₄ , filtered and concentrated to give an oil. Purification by automated silica gel column chromatography (5-50% EtOAc in hexanes) gave the title compound (568 mg, 82%) as a yellow crystalline solid: ¹ H NMR (300 MHz, CDCl ₃ ) δ 7.43 (td, J=8.0, 1.5Hz, 2H), 7.11 (td, J=8.1, 4.9Hz, 2H), 6.83 (dd, J=8.1, 1 .4 Hz, 2H), 5.06-4.82 (m, 1H), 4.74 (d, J=1.2 Hz, 1H), 3.81 (s, 3H), 3.80 (s , 3H), 3.20 (s, 3H), 3.04 (s, 3H), 2.86 (d, J=9.5 Hz, 1H), 0.97 (d, J=6.4 Hz , 3H); ¹³ C NMR (126 MHz, CDCl ₃ ) δ 152.89, 152.82, 146.94, 145.53, 139.56, 138.92, 123.32, 123.26, 122.01, 119.01 , 111.30, 79.20, 77.22, 60.07, 59.26, 55.77, 55.64, 18.34; HRMS-ESI (m/z) ([M+Na] ⁺ ) calculated for C ₁₉ H ₂₄ O ₆ Na, 371.1465; found 371,1456.

[0089] Example 31, step 2: preparation of 1,1-bis(2,3-dimethoxyphenyl)propan-2-one.

[0090] To a solution of (S)-1,1-bis(2,3-dimethoxyphenyl)propane-1,2-diol (560 mg, 1.61 mmol) in anhydrous CH ₂ Cl ₂ (8 ml) at 0° C was added triethylsilane (770 μl, 4.82 mmol) and trifluoroacetic acid (TFA, 124 μl, 1.61 mmol). The resulting solution was stirred at 0° C. for 2 h, then removed from the cold bath and stirred for 2 h. TFA (248 μl, 3.2 mmol) was added and then the reaction was stirred overnight with it. The reaction was diluted with water (25 ml) and was extracted using CH ₂ Cl ₂ (3×25 ml). The organic extracts were dried over Na ₂ SO ₄ , filtered and concentrated to give an oil. Purification by automated silica gel column chromatography (5-25% acetone in hexanes) gave the title compound (396 mg, 75%) as a white solid: ¹ H NMR (300 MHz, CDCl ₃ ) δ 6.99 ( t, J=8.0 Hz, 2H), 6.87 (dd, J=8.2, 1.5 Hz, 2H), 6.67-6.54 (m, 2H), 5.86 (s , 1H), 3.87 (s, 6H), 3.75 (s, 6H), 2.25 (s, 3H); ¹³ C NMR (126 MHz, CDCl ₃ ) δ 207.18, 152.69, 147.02, 132.23, 123.74, 121.61, 111.64, 60.36, 55.74, 51.96 , 29.80; HRMS-ESI (m/z) ([M+Na] ⁺ ) calculated for C ₁₉ H ₂₂ O ₅ Na, 353.1359; found 353,1353.

[0091] Example 31, step 3: preparation of 1,1-bis(2,3-dimethoxyphenyl)propan-2-ol.

[0092] Sodium borohydride (61 mg, 1.6 mmol ). The resulting solution was stirred with it for 20 h, then extinguished with saturated NH ₄ Cl (1 ml), diluted with water (20 ml) and was extracted using CH ₂ Cl ₂ (3×20 ml). The organic extracts were combined, dried over Na ₂ SO ₄ , filtered and concentrated to give the title compound (360 mg, 100%) as an oil: ¹ H NMR (300 MHz, CDCl ₃ ) δ 7.16-6 .88 (m, 4H), 6.79 (ddd, J=9.6, 7.8, 1.9 Hz, 2H), 4.81 (d, J=8.3 Hz, 1H), 4, 53-4.32(m, 1H), 3.84(s, 3H), 3.84(s, 3H), 3.77(s, 3H), 3.76(s, 3H), 2.04 (d, J=4.2 Hz, 1H), 1.22 (d, J=6.2 Hz, 3H); ¹³ C NMR (126 MHz, CDCl ₃ ) δ 152.98, 152.83, 147.71, 147.04, 136.17, 135.33, 123.94, 123.62, 120.96, 120.84 , 110.76, 110.48, 70.32, 60.26, 60.20, 55.66, 55.63, 45.11, 21.80; IR (blank film) 3451, 2935, 2833, 1582, 1473, 1428, 1266, 1215, 1167, 1125, 1088, 1068, 1004, 964, 908, 835, 809, 787, 748, 728.

[0093] Example 4A: preparation of (S)-(S)-1,1-diphenylpropan-2-yl 2-((tert-butoxycarbonyl)amino)-propanoate.

[0094] To a solution of (S)-1,1-diphenylpropan-2-ol (317 mg, 1.493 mmol) in DCM (15 ml) at 0°C was added (S)-2-((tert-butoxycarbonyl)amino) propanoic acid (Boc-Ala-OH; 311 mg, 1.64 mmol) and N,N-dimethylpyridin-4-amine (DMAP; 18.2 mg, 0.149 mmol) followed by hydrochloride N ¹ -((ethylimino) methylene)-N ³ ,N ³ -dimethylpropane-1,3-diamine (EDC; 573 mg, 2.99 mmol) and the reaction mixture was stirred at room temperature overnight and concentrated to give a yellow oil. The crude material was purified by flash column chromatography (SiO ₂ , 1->10% acetone in hexanes) to give the title compound (433 mg, 75%) as a colorless oil: ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.42-7.07 (m, 10H), 5.80 (dc, J=10.1, 6.1 Hz, 1H), 4.97 (d, J=8.0 Hz, 1H ), 4.19-4.06 (m, 1H), 4.03 (d, J=10.1 Hz, 1H), 1.41 (s, 9H), 1.23 (d, J=6, 1 Hz, 3H), 0.76 (d, J=7.2 Hz, 3H); ¹³ C NMR (101 MHz, CDCl ₃ ) δ 172.83, 154.96, 141.52, 141.26, 128.79, 128.50, 128.10, 128.08, 126.91, 126.67 , 79.62, 73.10, 57.98, 49.21, 28.33, 19.31, 17.98; ESFMS m/z 384 ([M+H] ⁺ ).

[0095] Example 5, Step 1: Preparation of (S)-1-(((5)-1,1-diphenylpropan-2-yl)oxy)-1-oxopropan-2-aminium chloride.

[0096] To a solution of (S)-(S)-1,1-diphenylpropan-2-yl 2-((tert-butoxycarbonyl)amino)propanoate (comp. 2; 433 mg, 1.13 mmol) in DCM (6 ml) was added 4 N HCl solution in dioxane (2.8 ml, 11.3 mmol) and the mixture was stirred for 3 h at room temperature. The solvent was evaporated under a stream of N ₂ to give the title compound (360 mg, 100%) as a white solid: ESFMS (m/z) 284 ([M+H] ⁺ ).

[0097] Example 5, Step 2: Preparation of (S)-(S)1,1-diphenylpropan-2-yl 2-(3-hydroxy-4-methoxypicolinamido)propanoate.

[0098] To (S)-1-(((S)-1,1-diphenylpropan-2-yl)oxy)-1-oxopropan-2-aminium chloride solution (comp. 46; 361 mg, 1.13 mmol ) and 3-hydroxy-4-methoxypicolinic acid (210 mg, 1.24 mmol) in DCM (11 ml) was added benzotriazol-1-yl-hydroxytripyrrolidinophosphonium hexafluorophosphate (PyBOP; 646 mg, 1.24 mmol) and N-ethyl- N-isopropylpropan-2-amine (DIPEA; 0.651 ml, 3.72 mmol) and the reaction mixture was stirred for 2 hours at room temperature. The solvent was evaporated and the crude oil was purified by flash column chromatography (SiO ₂ , 1->50% acetone in hexanes) to give the title compound (340 mg, 70%) as a white foam: ¹ H NMR ( 400 MHz, CDCl ₃ ) δ 12.10 (s, 1H), 8.34 (d, J=8.0 Hz, 1H), 7.98 (d, J=5.2 Hz, 1H), 7, 38-7.06 (m, 10H), 6.86 (d, J=5.3, 1H), 5.83 (dc, J=10.1, 6.1 Hz, 1H), 4.52 ( dc, J=8.1, 7.2 Hz, 1H), 4.06 (d, J=10.2 Hz, 1H), 3.93 (s, 3H), 1.26 (d, J=6 .1 Hz, 3H), 0.97 (d, J=7.2 Hz, 3H); ¹³ C NMR (101 MHz, CDCl ₃ ) δ 171.67, 168.53, 155.34, 148.72, 141.38, 141.13, 140.40, 130.48, 128.80, 128.50 , 128.10, 128.03, 126.95, 126.70, 109.39, 73.57, 57.93, 56.07, 47.85, 19.24, 17.61; HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₅ H ₂₇ N ₂ O ₅ , 435.1920; found 435,1925.

[0099] Example 6A: preparation of (S)-(S)-1,1-diphenylpropan-2-yl 2-(3-acetoxy-4-methoxypicolinamido)propanoate.

[00100] To a solution of (S)-(S)-1,1-diphenylpropan-2-yl 2-(3-hydroxy-4-methoxypicolinamido)-propanoate (comp. 90; 70.0 mg, 0.161 mmol), Et ₃ N (44.9 µl, 0.332 mmol) and DMAP (3.94 mg, 0.032 mmol) in DCM (3.2 ml) was added acetyl chloride (17.2 µl, 0.242 mmol) at room temperature and the reaction mixture was stirred for 2 h. The solvent was evaporated and the resulting crude oil was purified by flash column chromatography (SiO ₂ , 1->40% acetone in hexanes) to give the title compound (75.0 mg, 97%) as a colorless oil : ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.41 (d, J=7.8 Hz, 1H), 8.30 (d, J=5.4 Hz, 1H), 7.38-7, 10 (m, 10H), 6.97 (d, J=5.4 Hz, 1H), 5.82 (dc, J=10.0, 6.2 Hz, 1H), 4.52 (dt, J =8.2, 7.1 Hz, 1H), 4.05 (d, J=10.1 Hz, 1H), 3.87 (s, 3H), 2.37 (s, 3H), 1.24 (d, J=6.1 Hz, 3H), 0.89 (d, J=7.1 Hz, 3H); ¹³ C NMR (101 MHz, CDCl ₃ ) δ 172.23, 168.89, 162.28, 159.42, 146.66, 141.55, 141.44, 141.25, 137.45, 128.77 , 128.50, 128.13, 128.11, 126.89, 126.67, 109.73, 73.32, 57.90, 56.27, 47.85, 20.75, 19.25, 17 .92; HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₇ H ₂₉ N ₂ O ₆ , 477.2025; found 477,2019.

[00101] Example 6B: preparation of (S)-(S)-1,1-diphenylpropan-2-yl 2-(3-(acetoxymethoxy)-4-methoxypicolinamido)propanoate.

[00102] To a suspension of (S)-(S)-1,1-diphenylpropan-2-yl 2-(3-hydroxy-4-methoxypicolinamido)-propanoate (comp. 90; 100 mg, 0.230 mmol) and K ₂ CO ₃ (63.6 mg, 0.460 mmol) in acetone (4.6 ml) was added bromomethyl acetate (33.9 μl, 0.345 mmol) at room temperature and the mixture was heated to 55°C for 3 h and then cooled to room temperature. The solvent was evaporated and the resulting crude material was purified by flash column chromatography (SiO ₂ , 1->40% acetone in hexanes) to give the title compound (94.0 mg, 80% yield) as a colorless oil: ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.25 (d, J=5.4 Hz, 1H), 8.22 (d, J=7.9 Hz, 1H), 7.34-7.09 ( m, 10H), 6.92 (d, J=5.4 Hz, 1H), 5.83 (dc, J=10.1, 6.2 Hz, 1H), 5.72 (d, J=0 .7 Hz, 2H), 4.60-4.49 (m, 1H), 4.06 (d, J=10.1 Hz, 1H), 3.88 (s, 3H), 2.05 (s , 3H), 1.25 (d, J=6.1 Hz, 3H), 0.91 (d, J=7.2 Hz, 3H); ¹³ C NMR (101 MHz, CDCl ₃ ) δ 172.33, 170.25, 162.88, 160.24, 145.70, 143.91, 142.54, 141.48, 141.25, 128.76 , 128.49, 128.12, 128.09, 126.89, 126.65, 109.56, 89.50, 73.27, 57.92, 56.17, 48.07, 20.86, 19 .25, 17.73; HRMS-ESI (m/z) [M+H] ⁺ calculated for C ₂₈ H ₃₁ N ₂ O ₇ , 507.2131; found 507.2125.

[00103] Example 6C: preparation of (S)-(S)-1,1-diphenylpropan-2-yl 2-(3-((isobutyryloxy)methoxy)-4-methoxypicolinamido)propanoate.

[00104] To a solution of (S)-(S)-1,1-diphenylpropan-2-yl 2-(3-hydroxy-4-methoxypicolinamido)-propanoate (comp. 90; 100 mg, 0.230 mmol) in acetone (4 .6 ml) sodium carbonate (Na ₂ CO ₃ ; 73.2 mg, 0.690 mmol), sodium iodide (NaI; 6.90 mg, 0.046 mmol) and chloromethyl 2-ethoxyacetate (62.9 mg, 0.460 mmol) were added. The mixture was heated to 55° C. overnight and then cooled to room temperature and the solvent was evaporated. The resulting residue was purified by flash column chromatography (SiO ₂ , 2->30% acetone in hexanes) to give the title compound (79.0 mg, 64%) as a colorless oil: ¹ H NMR (400 MHz , CDCl ₃ ) δ 8.28 (d, J=7.9 Hz, 1H), 8.25 (d, J=5.3 Hz, 1H), 7.36-7.08 (m, 10H), 6.92 (d, J=5.4 Hz, 1H), 5.83 (dc, J=10.1, 6.2 Hz, 1H), 5.79-5.69 (m, 2H), 4 .62-4.44 (m, 1H), 4.06 (d, J=10.1 Hz, 1H), 3.86 (s, 3H), 2.53 (hept., J=7.0 Hz , 1H), 1.25 (d, J=6.2 Hz, 3H), 1.13 (d, J=7.0 Hz, 6H), 0.91 (d, J=7.2 Hz, 3H ); ¹³ C NMR (101 MHz, CDCl ₃ ) δ 176.22, 172.34, 162.85, 160.23, 145.55, 144.16, 142.18, 141.48, 141.26, 128.76 , 128.49, 128.12, 128.09, 126.89, 126.65, 109.48, 89.90, 73.26, 57.93, 56.12, 48.07, 33.85, 19 .26, 18.68, 17.74; HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₀ H ₃₅ N ₂ O ₇ , 535.2444; found 535.2431.

[00105] Example A: Evaluation of fungicidal activity: Wheat leaf spot (Zymoseptoria tritici; Bayer code SEPTTR):

[00106] Technical grade materials were dissolved in acetone, which was then mixed with 9 volumes of water (H ₂ O) containing 110 ppm Triton X-100. Fungicide solutions were applied to wheat seedlings using an automated runoff spray booth. All sprayed plants were allowed to air dry before further manipulations. All fungicides were evaluated using the above method for their activity against all target diseases, unless otherwise indicated. Wheat leaf spot and leaf rust activity was also evaluated using caterpillar spray application, in which case the fungicides were formulated as EC formulations containing 0.1% Try col 5941 in spray solutions.

[00107] Wheat plants (Yuma varietal) were grown from seed in a greenhouse in 50% mineral soil/50% soilless Metro mix until full first leaf appearance, 7-10 seedlings per pot. These plants were inoculated with an aqueous suspension of Zymoseptoria tritici spores either before or after fungicidal treatment. After inoculation, the plants were kept at 100% relative humidity (one day in a dark humid chamber followed by two to three days in a lighted humid chamber at 20° C.) to allow spores to germinate and infect the leaf. The plants were then transferred to a greenhouse set at 20°C for disease development. When disease symptoms were fully developed on the first leaves of untreated plants, infection levels were assessed on a disease severity scale from 0 to 100 percent. Percent disease control was calculated using the ratio of disease severity on treated plants to untreated plants.

[00108] Example B: Evaluation of fungicidal activity: wheat leaf rust (Puccinia triticina; synonym Puccinia recondita f. sp. tritici; Bayer code PUCCRT):

[00109] Wheat plants (Yuma varietal) were grown from seed in a greenhouse in 50% mineral soil/50% Metro soilless mix until full first leaf appearance, 7-10 seedlings per pot. These plants were inoculated with an aqueous suspension of Puccinia triticina spores either before or after fungicidal treatment. After inoculation, the plants were kept in a dark, humid room at 22° C. with 100% relative humidity overnight to allow spores to germinate and infect the leaf. The plants were then transferred to a greenhouse set at 24°C for disease development. Fungicidal formulation, application and disease evaluation followed the procedures as described in Example A.

[00110] Example C: Evaluation of Fungicidal Activity: Wheat Septoria (Leptosphaeria nodorum; Bayer code LEPTNO):

[00111] Wheat plants (Yuma varietal) were grown from seed in a greenhouse in 50% mineral soil/50% soilless Metro mix until full first leaf appearance, 7-10 seedlings per pot. These plants were inoculated with an aqueous suspension of Leptosphaeria nodorum spores 24 hours after the fungicidal treatment. After inoculation, the plants were kept at 100% relative humidity (one day in a dark humid chamber followed by two days in a lighted humid chamber at 20° C.) to allow spores to germinate and infect the leaf. The plants were then transferred to a greenhouse set at 20°C for disease development. Fungicidal formulation, application and disease evaluation followed the procedures as described in Example A.

[00112] Example D: Evaluation of Fungicidal Activity: Apple Scab (Venturia inaequalis; Bayer code VENTFN):

[00113] Apple seedlings (variety Mcintosh) were grown in Metro soilless mix, one plant per pot. Seedlings with two growing young leaves at the top (older leaves at the bottom of the plants were cut off) were used in the test. Plants were inoculated with Venturia inaequalis spore suspension 24 hours after fungicidal treatment and kept in a humid chamber at 22°C with 100% relative humidity for 48 hours and then transferred to a greenhouse set at 20°C for disease development. Fungicide formulation, application and disease assessment on sprayed leaves followed the procedures as described in Example A.

[00114] Example E: Evaluation of Fungicidal Activity: Sugar Beet Leaf Blight (Cercospora beticola; Bayer code CERCBE):

[00115] Sugar beet plants (variety HH88) were grown in Metro soilless mix and pruned regularly to maintain uniform plant size prior to testing. Plants were inoculated with spore suspension 24 hours after fungicidal treatment. The inoculated plants were kept in a humid chamber at 22° C. for 48 hours, then incubated in a greenhouse set at 24° C. under a transparent plastic hood with ventilation through the bottom until disease symptoms were fully developed. Fungicide formulation, application and disease assessment on sprayed leaves followed the procedures as described in Example A.

[00116] Example F: Evaluation of fungicidal activity: Asian soybean rust (Phakopsora pachyrhizi; Bayer code PHAKPA)

[00117] Commercial grade materials were dissolved in acetone, which was then mixed with nine volumes of H ₂ O containing 0.011% Tween 20. Fungicide solutions were applied to soybean seedlings using an automated runoff spray booth. All sprayed plants were allowed to air dry before further manipulations.

[00118] Soybean plants (variety Williams 82) were grown in Metro soilless mix, one plant per pot. Shoots at the age of two weeks were used for testing. Plants were inoculated either 3 days before or 1 day after the fungicidal treatment. Plants were incubated for 24 hours in a dark, humid room at 22°C and 100% relative humidity, then transferred to a greenhouse at 23°C to develop the disease. Disease severity was assessed on sprayed leaves.

[00119] Example G: Evaluation of Fungicidal Activity: Barley Blight (Rhyncosporium secalis; Bayer code RHYNSE):

[00120] Barley seedlings (variety Harrington) were grown in Metro soilless mix, 8-12 plants per pot, and used in the test when the first leaf was fully developed. Test plants were inoculated with an aqueous suspension of Rhyncosporium secalis spores 24 hours after fungicidal treatment. After inoculation, the plants were kept in a humid room at 22°C with 100% relative humidity for 48 hours. The plants were then transferred to a greenhouse set at 20°C for disease development. Fungicide formulation, application and disease assessment on sprayed leaves followed the procedures as described in Example A.

[00121] Example H: Evaluation of Fungicidal Activity: Rice Blast (Pyricularia oryzae; Bayer code PYRIOR):

[00122] Rice seedlings (variety Japonica) were grown in Metro soilless mix, 8-14 plants per pot, and used in the test, aged 12 to 14 days. Test plants were inoculated with an aqueous suspension of Pyricularia oryzae spores 24 hours after fungicidal treatment. After inoculation, the plants were kept in a humid room at 22° C. with 100% relative humidity for 48 hours to allow the spores to germinate and infect the leaf. The plants were then transferred to a greenhouse set at 24°C for disease development. Fungicide formulation, application and disease assessment on sprayed leaves followed the procedures as described in Example A.

[00123] Example I: Evaluation of Fungicidal Activity: Tomato Alternaria (Alternaria solani; Bayer code ALTESO):

[00124] Tomato plants (Outdoor Girl variety) were grown in Metro soilless mix, one plant per pot, and used at 12 to 14 days of age. Test plants were inoculated with an aqueous suspension of Alternaria solani spores 24 hours after fungicidal treatment. After inoculation, the plants were kept in a humid room at 22° C. with 100% relative humidity for 48 hours to allow the spores to germinate and infect the leaf. The plants were then transferred to a greenhouse at 22°C to develop the disease. Fungicide formulation, application and disease assessment on sprayed leaves followed the procedures as described in Example A.

[00125] Example J: Evaluation of Fungicidal Activity: Cucumber Anthracnose (Colletotrichum lagenarium; Bayer code COLLLA):

[00126] Cucumber seedlings (Bush Pickle varietal) were grown in Metro soilless mix, one plant per pot, and used in the test at 12 to 14 days of age. Test plants were inoculated with an aqueous suspension of Colletotrichum lagenarium spores 24 hours after fungicidal treatment. After inoculation, the plants were kept in a humid room at 22° C. with 100% relative humidity for 48 hours to allow the spores to germinate and infect the leaf. The plants were then transferred to a greenhouse set at 22°C for disease development. Fungicide formulation, application and disease assessment on sprayed leaves followed the procedures as described in Example A.

Table 1. Structure of the compound, method of preparation and appearance

conn. no. Structure Obtained according to the example Appearance 1

Example 1; example 3A; example 4A White solid 2

Example 1; example 2A; example 3A; example 4A colorless oil 3

Example 1; example 2A; example 3A; example 4A colorless oil 4

Example 1; example 2A; example 3A; example 4A Clear colorless oil 5

Example 1; example 2B; example 3A; example 4A colorless oil 6

Example 1; example 2B; example 3A; example 4A colorless oil 7

Example 1; example 2A; example 3A; example 4A colorless oil 8

Example 1; example 2C; example 3A; example 4A colorless oil 9

Example 1; example 2A; example 3A; example 4A colorless oil 10

Example 1; example 2A; example 3A; example 4A colorless oil eleven

Example 1; example 2A; example 3A; example 4A colorless oil 12

Example 3E; example 4A colorless oil 13

Example 3E; example 4A colorless oil 14

Example 1; example 3C; example 4A colorless oil 15

Example 1; example 3C; example 4A colorless oil 16

Example 1; example 2A; example 3A; example 4A colorless oil 18

Example 3F; example 4A colorless oil 19

Example 1; example 2A; example 3A; example 4A colorless oil 20

Example 1; example 2A; example 3A; example 4A clear oil 21

Example 1; example 2A; example 3A; example 4A clear oil 22

Example 1; example 2A; example 3A; example 4A clear oil 23

Example 1; example 2A; example 3A; example 4A clear oil 24

Example 1; example 3C; example 4A sticky wax 25

Example 1; example 3C; example 4A sticky wax 26

Example 1; example 3C; example 4A sticky wax 27

Example 1; example 3C; example 4A sticky wax 28

Example 1; example 3C; example 3D, steps 1-2; example 4A white foam 29

Example 1; example 3C; example 3D, steps 1-3; example 4A sticky wax 31

Example 3F; example 4A clear oil 33

Example 1; example 3B; example 4A White solid 34

Example 1; example 3B; example 4A White solid 35

Example 1; example 2A; example 3A; example 4A White solid 36

Example 1; example 3b; example 4A white foam 37

Example 1; example 2A; example 3A; example 4A Clear colorless oil 38

Example 1; example 2A; example 3A; example 4A Clear colorless oil 39

Example 1; example 2A; example 3A; example 4A Clear colorless oil 40

Example 1; example 2A; example 3A; example 4A white foam 43

Example 1; example 2A; example 3A; example 4A White solid 44

Example 1; example 2A; example 3A; example 4A White solid 45

Example 5, step 1 White solid 46

Example 5, step 1 colorless oil 47

Example 5, step 1 colorless oil 48

Example 5, step 1 Pale yellow oil 49

Example 5, step 1 colorless oil 50

Example 5, step 1 colorless oil 51

Example 5, step 1 colorless oil 52

Example 5, step 1 colorless oil 53

Example 5, step 1 colorless oil 54

Example 5, step 1 colorless oil 55

Example 5, step 1 colorless oil 56

Example 5, step 1 colorless oil 57

Example 5, step 1 colorless oil 58

Example 5, step 1 colorless oil 59

Example 5, step 1 colorless oil 60

Example 5, step 1 colorless oil 61

Example 5, step 1 White solid 63

Example 5, step 1 colorless oil 64

Example 5, step 1 colorless oil 65

Example 5, step 1 sticky oil 66

Example 5, step 1 sticky oil 67

Example 5, step 1 sticky oil 68

Example 5, step 1 sticky wax 69

Example 5, step 1 sticky wax 70

Example 5, step 1 sticky wax 71

Example 5, step 1 White solid 72

Example 5, step 1 White solid 73

Example 5, step 1 White solid 74

Example 5, step 1 White solid 75

Example 5, step 1 White solid 77

Example 5, step 1 White solid 78

Example 5, step 1 White solid 79

Example 5, step 1 White solid 80

Example 1; example 3B; example 4A; example 5, stage 1 sticky oil 81

Example 5, step 1 sticky oil 83

Example 5, step 1 colorless oil 84

Example 5, step 1 Clear colorless oil 85

Example 5, step 1 Clear colorless oil 86

Example 5, step 1 White solid 87

Example 5, step 1 White solid 88

Example 5, step 1 White solid 89

Example 5, step 2 White solid 90

Example 5, step 2 white foam 91

Example 5, step 2 colorless oil 92

Example 5, step 2 white foam 93

Example 5, step 2 white foam 95

Example 5, step 2 colorless oil 96

Example 5, step 2 white foam 97

Example 5, step 2 colorless oil 98

Example 5, step 2 colorless oil 99

Example 5, step 2 colorless oil 100

Example 5, step 2 colorless oil 101

Example 5, step 2 colorless oil 102

Example 5, step 2 colorless oil 103

Example 5, step 2 colorless oil 104

Example 5, step 2 colorless oil 105

Example 5, step 2 colorless oil 106

Example 5, step 2 Colorless gel 107

Example 5, step 2 Colorless gel 109

Example 5, step 2 colorless oil 110

Example 5, step 2 Clear colorless oil 111

Example 5, step 2 Clear colorless oil 112

Example 5, step 2 Clear colorless oil 113

Example 5, step 2 White solid 114

Example 5, step 2 White solid 115

Example 5, step 2 White solid 116

Example 5, step 2 White solid 117

Example 5, step 2 white foam 118

Example 5, step 2 white foam 119

Example 5, step 2 white foam 120

Example 5, step 2 white foam 121

Example 5, step 2 white foam 122

Example 5, step 2 white foam 123

Example 5, step 2 white foam 124

Example 5, step 2 white foam 125

Example 5, step 2 White solid 127

Example 5, step 2 White solid 128

Example 5, step 2 White solid 129

Example 5, step 2 White solid 130

Example 5, step 2 Clear colorless oil 131

Example 5, step 2 Clear colorless oil 132

Example 5, step 2 colorless foam 133

Example 5, step 2 colorless foam 135

Example 5, step 2 Colorless sticky semi-solid 136

Example 5, step 2 white foam 137

Example 5, step 2 white foam 138

Example 6B Colorless semi-solid 139

Example 6A colorless oil 140

Example 6A white foam 141

Example 6B white foam 142

Example 6C white foam 143

Example 6A colorless oil 144

Example 6B colorless oil 145

Example 6A colorless oil 146

Example 6B colorless oil 147

Example 6B colorless oil 148

Example 6B colorless oil 149

Example 6B colorless oil 150

Example 6A colorless oil 152

Example 6A colorless oil 153

Example 6B colorless oil 155

Example 6A colorless oil 156

Example 6A colorless oil 157

Example 6A colorless oil 158

Example 6B colorless oil 159

Example 6B colorless oil 160

Example 6B colorless oil 161

Example 6A colorless oil 162

Example 6A colorless oil 163

Example 6B colorless oil 164

Example 6B colorless oil 165

Example 6A colorless oil 166

Example 6A colorless oil 167

Example 6A colorless oil 168

Example 6A colorless oil 169

Example 6B colorless oil 170

Example 6B colorless oil 171

Example 6B colorless oil 173

Example 6A colorless oil 174

Example 6A colorless oil 175

Example 6B colorless oil 176

Example 6B colorless oil 178

Example 6B Clear colorless oil 179

Example 6B Clear colorless oil 180

Example 6B Clear colorless oil 181

Example 6B white foam 182

Example 6A colorless oil 183

Example 6B White solid 184

Example 6B White solid 185

Example 6B White solid 186

Example 6B White solid 187

Example 6A White solid 188

Example 6A White solid 189

Example 6A White solid 190

Example 6A White solid 191

Example 6B white foam 192

Example 6B white foam 193

Example 6B sticky wax 194

Example 6B white foam 195

Example 6B white foam 196

Example 6B white foam 197

Example 6B white foam 198

Example 6B sticky wax 199

Example 6B White solid 201

Example 6B White solid 202

Example 6B White solid 203

Example 6B White solid 204

Example 6A White solid 206

Example 6A White solid 207

Example 6A White solid 208

Example 6A Clear colorless oil 209

Example 6A Slightly cloudy colorless oil 210

Example 6A Slightly cloudy colorless oil 211

Example 6C Clear colorless oil 212

Example 6C Colorless transparent film and opaque oil 213

Example 6A Clear, colorless viscous oil and semi-solid 214

Example 6B Clear colorless oil 215

Example 6A Pale yellow oil 216

Example 6A Pale yellow oil 217

Example 6A Pale yellow oil 218

Example 6B Pale yellow oil 219

Example 6B Pale yellow oil 220

Example 6B Pale yellow oil 221

Example 6B white foam 222

Example 6B white foam 223

Example 6A white foam 224

Example 6A white foam 225

Example 6B Slightly opaque colorless oil 226

Example 1; example 2D, steps 1-2; example 3A; example 4A White semi-solid 227

Example 5, step 1 White glass 228

Example 5, step 2 colorless foam 229

Example 6A Clear colorless oil 230

Example 6B Clear colorless oil 232

Example 5, step 1 White semi-solid 233

Example 1; example 2A; example 3A; example 4A Clear colorless viscous oil 234

Example 1; example 2A; example 3A; example 4A. Clear colorless oil 235

Example 1; example 2A; example 3A; example 4A. Clear colorless oil 236

Example 1; example 2A; example 3A; example 4A. Clear colorless oil 237

Example 1; example 2A; example 3A; example 4A. Clear colorless oil 238

Example 1; example 2A; example 3A; example 4A. Slightly cloudy colorless viscous oil 239

Example 1; example 2A; example 3A; example 4A. Slightly cloudy colorless viscous oil 240

Example 1; example 2A; example 3A; example 4A. white foam 241

Example 3H steps 1-2; example 4A. colorless oil 242

Example 3G, steps 1 and 2; example 4A colorless oil 243

Example 3G, steps 1 and 2; example 4A colorless oil 244

Example 4A colorless oil 245

Example 1; example 3C; example 4A. white foam 246

Example 1; example 2A; example 3A; example 4A. white foam 247

Example 1; example 3C; example 4A. white foam 248

Example 1; example 2A; example 3A; example 4A. white foam 249

Example 3G, steps 1 and 2; example 4A white foam 250

Example 1; example 2A; example 3A; example 4A. White semi-solid 251

Example 1; example 2A; example 3A; example 4A. White semi-solid 252

Example 1; example 2A; example 3A; example 4A. White semi-solid 253

Example 1; example 2A; example 3A; example 4A. Clear colorless oil 254

Example 1; example 2A; example 3A; example 4A. Clear colorless oil 255

Example 1; example 2A; example 3A; example 4A. Clear colorless oil 256

Example 1; example 2A; example 3A; example 4A. Clear colorless oil 257

Example 1; example 2A; example 3A; example 4A. Clear colorless oil 258

Example 31, Example 4A white foam 259

Example 1; example 2A; example 3A; example 4A. white foam 260

Example 1; example 2A; example 3A; example 4A. colorless oil 261

Example 1; example 2A; example 3A; example 4A. colorless oil 262

Example 1; example 2A; example 3A; example 4A. colorless oil 263

Example 1; example 2A; example 3A; example 4A. colorless oil 264

Example 1; example 2A; example 3A; example 4A. white foam 265

Example 1; example 2A; example 3A; example 4A. colorless oil 266

Example 1; example 2A; example 3A; example 4A. sticky wax 267

Example 1; example 2A; example 3A; example 4A. Sticky wax. 268

Example 31, Example 4A Oil 269

Example 31, Example 4A Oil 270

Example 1; example 2A; example 3A; example 4A colorless oil 271

Example 1; example 2A; example 3A; example 4A colorless oil 272

Example 1; example 2A; example 3A; example 4A colorless oil 273

Example 1; example 2A; example 3A; example 4A colorless oil 274

Example 1; example 2A; example 3A; example 4A colorless oil 275

Example 3F; example 4A colorless oil 276

Example 3F; example 4A colorless oil 277

Example 3F; example 4A colorless oil 278

Example 3F; example 4A colorless oil 279

Example 3F; example 4A colorless oil 280

Example 3F; example 4A colorless oil 281

Example 3F; example 4A colorless oil 282

Example 3F; example 4A colorless oil 283

Example 3F; example 4A colorless oil 284

Example 3F; example 4A colorless oil 285

Example 3F; example 4A colorless oil 286

Example 3F; example 4A colorless oil 287

Example 3F; example 4A colorless oil 288

Example 3F; example 4A white foam 289

Example 3F; example 4A Sticky yellow wax 290

Example 3F; example 4A white foam 291

Example 3F; example 4A Sticky yellow wax 292

Example 1; example 2A; example 3A; example 4A colorless oil 293

Example 1; example 2A; example 3A; example 4A colorless oil 294

Example 1; example 2A; example 3A; example 4A colorless oil 295

Example 3F; example 4A colorless oil 296

Example 3F; example 4A colorless oil 297

Example 3F; example 4A colorless oil 298

Example 3F; example 4A colorless oil 299

Example 3F; example 4A colorless oil 300

Example 3F; example 4A colorless oil 301

Example 3F; example 4A colorless oil 302

Example 3F; example 4A colorless oil 303

Example 3F; example 4A colorless oil 304

Example 3F; example 4A colorless oil 305

Example 3F; example 4A colorless oil 306

Example 3F; example 4A colorless oil 307

Example 3F; example 4A colorless oil 308

Example 3F; example 4A thick oil 309

Example 3F; example 4A colorless oil 310

Example 5, stage 1. white powder 311

Example 5, stage 1. white powder 312

Example 5, stage 1. Clear colorless thick oil 313

Example 5, stage 1. white powder 314

Example 5 stage 1. White semi-solid 315

Example 5 stage 1. White semi-solid 316

Example 5, stage 1. Clear glass 317

Example 1; example 2A; example 3A; example 4A, example 5, step 1. Pale purple sticky wax 318

Example 5 stage 1. colorless oil 319

Example 5, step 1 white foam 320

Example 5, step 1 white foam 321

Example 5, step 1 White solid 322

Example 5, stage 1. colorless oil 323

Example 5, stage 1. yellow oil 324

Example 5, stage 1. yellow oil 325

Example 5, stage 1. yellow oil 326

Example 5, stage 1. yellow oil 327

Example 5, step 1 white foam 328

Example 5, step 1 white foam 329

Example 5, step 1 white foam 330

Example 5, step 1 white foam 331

Example 5, step 1 white foam 332

Example 5, stage 1. Clear colorless oil 333

Example 5, stage 1. Light brown oil 334

Example 5, stage 1. Pale yellow oil 335

Example 5, stage 1. Pale yellow oil 336

Example 5, stage 1. White powdery substance 337

Example 5, stage 1. Clear colorless oil 338

Example 5, stage 1. White powdery substance 339

Example 5, stage 1. Clear colorless oil 340

Example 5, stage 1. White solid 341

Example 5, stage 1. thick oil 342

Example 5, stage 1. White solid 343

Example 5, stage 1. White solid 344

Example 5, stage 1. White solid 345

Example 5, stage 1. White solid 346

Example 5, stage 1. thick oil 347

Example 5, stage 1. White solid 348

Example 5, stage 1. White solid 349

Example 5, step 1 Oil 350

Example 5, step 1 Oil 351

Example 5, step 1 Oil 352

Example 5, step 1 colorless oil 353

Example 5, step 1 colorless oil 354

Example 5, step 1 colorless oil 355

Example 5, step 1 colorless oil 356

Example 5, step 1 colorless oil 357

Example 5, step 1 colorless oil 358

Example 5, step 1 colorless oil 359

Example 5, step 1 colorless oil 360

Example 5, step 1 colorless oil 361

Example 5, step 1 colorless foam 362

Example 5, step 1 colorless foam 363

Example 5, step 1 colorless oil 364

Example 5, step 1 colorless oil 365

Example 5, step 1 white foam 366

Example 5, stage 1. sticky wax 367

Example 5, stage 1. sticky wax 368

Example 5, stage 1. sticky wax 369

Example 5, stage 1. sticky wax 370

Example 5, step 1 white foam 371

Example 5, step 1 white foam 372

Example 5, step 1 white foam 373

Example 5, step 1 white foam 374

Example 5, step 1 white foam 375

Example 5, step 1 colorless oil 376

Example 5, step 1 colorless oil 377

Example 5, stage 1. thick oil 378

Example 5, stage 1. thick oil 379

Example 5, stage 1. White solid 380

Example 5, stage 1. thick oil 381

Example 5, stage 1. thick oil 382

Example 5, stage 1. white foam 383

Example 5, stage 1. White solid 384

Example 5, stage 1. white foam 385

Example 5, stage 1. white foam 386

Example 5 stage 2. Matte white solid and clear oil 387

Example 5 stage 2. Matte white solid and clear oil 388

Example 5, step 2. Clear colorless oil 389

Example 5, step 2. colorless foam 390

Example 5, step 2. colorless foam 391

Example 5, step 2. Clear colorless oil 392

Example 5, step 2. semi-solid 393

Example 5, step 2. white foam 394

Example 5 stage 2. Colorless frothy oil 395

Example 5, step 2. white foam 396

Example 5, step 2 white foam 397

Example 5, step 2 white foam 398

Example 5, step 2 white foam 399

Example 5, step 2. white foam 400

Example 5, step 2. white foam 401

Example 5, step 2. white foam 402

Example 5, step 2. white foam 403

Example 5, step 2 colorless oil 404

Example 5, step 2 colorless oil 405

Example 5, step 2 white foam 406

Example 5, step 2 white foam 407

Example 5, step 2 white foam 408

Example 5, step 2 white foam 409

Example 5, step 2 white foam 410

Example 5, step 2 white foam 411

Example 5, step 2 white foam 412

Example 5, step 2 Oil 413

Example 5, step 2. white foam 414

Example 5, step 2. thick oil 415

Example 5, step 2. white foam 416

Example 5, step 2. white foam 417

Example 5, step 2. white foam 418

Example 5, step 2. white foam 419

Example 5, step 2. white foam 420

Example 5, step 2. colorless foam 421

Example 5, step 2. Clear colorless oil 422

Example 5, step 2. Clear colorless oil 423

Example 5, step 2. colorless foam 424

Example 5, step 2. colorless foam 425

Example 5, step 2. Clear colorless oil 426

Example 5, step 2. Clear colorless oil 427

Example 5, step 2. Clear colorless oil 428

Example 5, step 2. white foam 429

Example 5, step 2. sticky wax 430

Example 5, step 2 Colorless gel 431

Example 5, step 2 Colorless gel 432

Example 5, step 2 Colorless gel 433

Example 5, step 2 Colorless gel 434

Example 5, step 2 colorless oil 435

Example 5, step 2 colorless oil 436

Example 5, step 2 colorless oil 437

Example 5, step 2 colorless oil 438

Example 5, step 2 colorless foam 439

Example 5, step 2 colorless foam 440

Example 5, step 2 colorless oil 441

Example 5, step 2 colorless oil 442

Example 5, step 2 white foam 443

Example 5, step 2. white foam 444

Example 5, step 2. white foam 445

Example 5, step 2. white foam 446

Example 5, step 2. white foam 447

Example 5, step 2 white foam 448

Example 5, step 2 white foam 449

Example 5, step 2 white foam 450

Example 5, step 2 white foam 451

Example 5, step 2 white foam 452

Example 5, step 2 colorless oil 453

Example 5, step 2 colorless oil 454

Example 5, step 2. white foam 455

Example 5, step 2. white foam 456

Example 5, step 2. white foam 457

Example 5, step 2. white foam 458

Example 5, step 2. white foam 459

Example 5, step 2. white foam 460

Example 5, step 2. white foam 461

Example 5, step 2. white foam 462

Example 6B. Slightly opaque colorless viscous oil 463

Example 6B. Slightly opaque colorless viscous oil 464

Example 6B. yellow oil 465

Example 6B. Clear colorless oil 466

Example 6B. Pale yellow oil 467

Example 6B. Pale yellow oil 468

Example 6A. Loose white powder 469

Example 6A. Clear colorless oil 470

Example 6A. Clear colorless oil 471

Example 6A. Clear colorless oil 472

Example 6B. white foam 473

Example 6B. sticky wax 474

Example 6B. colorless oil 475

Example 6A. white foam 476

Example 6B. white foam 477

Example 6A. white foam 478

Example 6A. white foam 479

Example 6A. white foam 480

Example 6B. white foam 481

Example 6B. white foam 482

Example 6B. white foam 483

Example 6B. white foam 484

Example 6B. white foam 485

Example 6A colorless oil 486

Example 6A colorless oil 487

Example 6B colorless oil 488

Example 6A. white foam 489

Example 6A. white foam 490

Example 6A. White wax 491

Example 6A. white foam 492

Example 6A. white foam 493

Example 6B white foam 494

Example 6C white foam 495

Example 6A white foam 496

Example 6A white foam 497

Example 6A Colorless film 498

Example 6A. white foam 499

Example 6A. white foam 500

Example 6A. white foam 501

Example 6A. white foam 502

Example 6A. white foam 503

Example 6A. white foam 504

Example 6A. white foam 505

Example 6A. Clear colorless oil 506

Example 6A. Clear colorless oil 507

Example 6A. Clear colorless oil 508

Example 6A. Clear colorless oil 509

Example 6A. Clear colorless oil 510

Example 6A. Clear colorless oil 511

Example 6A. Clear colorless oil 512

Example 6a. Clear colorless oil 513

Example 6b. Clear colorless oil 514

Example 6b. Clear colorless oil 515

Example 6B. Clear colorless oil 516

Example 6B. Clear colorless oil 517

Example 6B. Clear colorless oil 518

Example 6B. Clear colorless oil 519

Example 6B. Clear colorless oil 520

Example 6B. Clear colorless oil 521

Example 6A. White foam. 522

Example 6A. Sticky white foam 523

Example 6A colorless oil 524

Example 6A colorless oil 525

Example 6A colorless oil 526

Example 6A colorless oil 527

Example 6A colorless foam 528

Example 6A colorless foam 529

Example 6A colorless foam 530

Example 6A colorless foam 531

Example 6A colorless oil 532

Example 6A colorless oil 533

Example 6A colorless oil 534

Example 6A colorless oil 535

Example 6A. white foam 536

Example 6A. white foam 537

Example 6A. white foam 538

Example 6A. white foam 539

Example 6A. white foam 540

Example 6A. white foam 541

Example 6A. white foam 542

Example 6A. white foam 543

Example 6A. white foam 544

Example 6A. white foam 545

Example 6A. white foam 546

Example 6A. white foam 547

Example 6A. white foam 548

Example 6A. white foam 549

Example 6A. white foam 550

Example 6A. white foam 551

Example 6A. white foam 552

Example 6A. white foam 553

Example 6A colorless foam 554

Example 6A colorless foam

conn. no. - connection number

Table 2. Analytical data

conn. no. MP (°C) IR (cm ^-1 ) MASS NMR (1H, 13C, 19F) 1 ... ... HRMS-ESI (m/z) [M] ⁺ calculated for C ₂₃ H ₂₉ NO ₅ , 399.2046; found 399,2048 ¹ H NMR (500 MHz, CDCl ₃ ) δ 7.53-7.41 (m, 4H), 7.32-7.23 (m, 4H), 7.23-7.13 (m, 2H), 6.01 (q, J=6.3 Hz, 1H), 4.98 (d, J=8.0 Hz, 1H), 4.13 (p, J=7.1 Hz, 1H), 2, 78 (s, 1H), 1.41 (s, 9H), 1.21 (d, J=6.3 Hz, 3H), 0.83 (d, J=7.3 Hz, 3H)
¹³ C NMR (126 MHz, CDCl ₃ ) δ 172.55, 154.95, 145.04, 142.86, 128.32, 128.30, 127.17, 127.11, 125.59, 125.52 , 79.83, 79.54, 75.16, 49.13, 28.29, 17.95, 14.38 2 ... ... ESIMS m/z 384.5 ([M+H] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.42-7.07 (m, 10H), 5.80 (dc, J=10.1, 6.1 Hz, 1H), 4.97 (d, J=8.0 Hz, 1H), 4.19-4.06 (m, 1H), 4.03 (d, J=10.1 Hz, 1H), 1.41 (s, 9H), 1, 23 (d, J=6.1 Hz, 3H), 0.76 (d, J=7.2 Hz, 3H)
¹³ C NMR (101 MHz, CDCl ₃ ) δ 172.83, 154.96, 141.52, 141.26, 128.79, 128.50, 128.10, 128.08, 126.91, 126.67 , 73.10, 57.98, 28.33, 19.31, 17.98 3 ... ~ ESIMS m/z 396.5 ([M+H] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.22-7.15 (m, 2H), 7.00 (ddd, J=3.5, 1.2, 0.6 Hz, 1H), 6, 97-6.89 (m, 3H), 5.52 (dc, J=7.3, 6.2 Hz, 1H), 4.99 (d, J=5.1 Hz, 1H), 4.63 (d, J=7.3 Hz, 1H), 4.29-4.18 (m, 1H), 1.43 (s, 9H), 1.28 (d, J=6.2 Hz, 3H) , 1.04 (d, J=7.2 Hz, 3H)
¹³ C NMR (101 MHz, CDCl ₃ ) δ 172.64, 143.87, 142.87, 126.75, 126.55, 125.98, 125.39, 124.58, 124.56, 79.69 , 74.40, 49.31, 47.46, 28.32, 18.74, 18.22 4 ... ... ESIMS m/z 420.6 ([M+H] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.31-7.16 (m, 4H), 6.97 (td, J=8.7, 7.0 Hz, 4H), 5.71 (dc, J=9.8, 6.1 Hz, 1H), 4.95 (d, J=8.0 Hz, 1H), 4.22-4.07 (m, 1H), 4.03 (d, J =9.8Hz, 1H), 1.42(s, 9H), 1.22(d, J=6.2Hz, 3H), 0.84(d, J=7.2Hz, 3H)
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -115.53, -115.94 5 ... ... ESIMS m/z 450.6 ([M+Na] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.37-7.19 (m, 10H), 6.01-5.89 (m, 1H), 5.02 (d, J=7.9 Hz, 1H), 4.27-4.10 (m, 1H), 3.38 (dc, J=8.9, 6.9 Hz, 1H), 3.25-3.13 (m, 1H), 1 .40 (d, J=2.1 Hz, 9H), 1.18 (t, J=7.0 Hz, 3H), 1.15-1.06 (m, 6H) 6 ... ... ESIMS m/z 436.6 ([M+Na] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.38-7.21 (m, 10H), 6.01-5.82 (m, 1H), 5.01 (d, J=8.0 Hz, 1H), 4.27-4.12(m, 1H), 3.15(s, 3H), 1.40(s, 9H), 1.15-1.07(m, 6H) 7 ... ... ESIMS m/z 456.5 ([M+H] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.36 (td, J=8.5, 6.1 Hz, 1H), 7.26-7.15 (m, 1H), 6.91-6, 68 (m, 4H), 5.86-5.73 (m, 1H), 4.92 (d, J=8.0 Hz, 1H), 4.66 (d, J=10.1 Hz, 1H ), 4.23-4.09 (m, 1H), 1.42 (s, 9H), 1.27 (d, J=6.1 Hz, 3H)
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -111.06 (d, J=7.6 Hz), -111.55 (d, J=7.5 Hz), -111.91 (dd, J= 7.9, 2.7 Hz), -112.72 (d, J=5.9 Hz) 8 ... ... ESIMS m/z 424.5 ([M+Na] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.48-7.41 (m, 4H), 7.38-7.19 (m, 6H), 5.97 (dc, J=25.6, 6 .5 Hz, 1H), 4.90 (d, J=7.8 Hz, 1H), 4.23-4.05 (m, 1H), 1.41 (s, 9H), 1.29 (dd , J=6.5, 1.0 Hz, 3H), 0.75 (d, J=7.2 Hz, 3H)
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -169.03 9 ... ... ESIMS m/z 444.6 ([M+H] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.22-7.09 (m, 4H), 6.91-6.65 (m, 4H), 5.70 (dc, J=9.8, 6 .1 Hz, 1H), 4.94 (d, J=8.0 Hz, 1H), 4.19-4.05 (m, 1H), 3.93 (d, J=9.8 Hz, 1H ), 3.76 (s, 3H), 3.74 (s, 3H), 1.42 (s, 9H), 1.21 (d, J=6.2 Hz, 3H), 0.83 (d , J=7.2 Hz, 3H)
¹³ C NMR (101 MHz, CDCl ₃ ) δ 172.84, 158.34, 158.22, 133.99, 133.81, 128.96, 114.10, 113.84, 79.64, 73.33 , 56.17, 55.22, 49.22, 28.31, 19.28, 18.19 10 ... ... ESIMS m/z 420.6 ([M+H] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.33-7.21 (m, 2H), 7.14-7.02 (m, 2H), 7.03-6.84 (m, 4H), 5.72 (dc, J=9.9, 6.2 Hz, 1H), 4.93 (d, J=8.0 Hz, 1H), 4.22-4.07 (m, 1H), 4 .03 (d, J=9.8 Hz, 1H), 1.42 (s, 9H), 1.24 (d, J=6.2 Hz, 3H), 0.84 (d, J=7, 1Hz, 3H)
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -112.14, -112.59 eleven ... ... ESIMS m/z 452.5 ([M+H] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.33-7.11 (m, 8H), 5.71 (dc, J=10.0, 5.9 Hz, 1H), 4.94 (d, J=8.0 Hz, 1H), 4.18-4.07 (m, 1H), 3.99 (d, J=9.9 Hz, 1H), 1.42 (d, J=1.7 Hz, 9H), 1.24 (d, J=6.2 Hz, 3H), 0.87-0.81 (m, 3H)
¹³ C NMR (101 MHz, CDCl ₃ ) δ 172.79, 154.94, 142.68, 142.43, 134.73, 134.43, 130.21, 129.93, 128.39, 128.32 , 127.49, 127.18, 126.28, 126.20, 79.79, 72.40, 57.09, 49.15, 28.30, 19.21, 18.04 12 ... ... ESIMS m/z 382.5 ([M+H] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.79-7.72 (m, 2H), 7.72-7.62 (m, 1H), 7.59-7.48 (m, 1H), 7.46-7.36(m, 2H), 7.36-7.25(m, 2H), 5.81-5.64(m, 1H), 5.09(s, 1H), 4, 55-4.34 (m, 1H), 4.33-4.18 (m, 1H), 1.46 (s, 9H), 1.45 (d, J=3.5 Hz, 3H), 0 .70 (d, J=6.3 Hz, 3H) 13 ... ... ESIMS m/z 398.6 ([M+H] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.33-7.21 (m, 4H), 7.15-7.04 (m, 4H), 5.15-5.03 (m, 1H), 5.01 (d, J=8.0 Hz, 1H), 4.35-4.24 (m, 1H), 4.27-4.15 (m, 1H), 1.44 (s, 9H) , 1.29 (d, J=7.2 Hz, 3H), 1.03 (d, J=6.4 Hz, 3H) 14 ... ... ESIMS m/z 542.5 ([M+H] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.46-7.36 (m, 4H), 7.17-7.07 (m, 4H), 5.71 (dc, J=9.7.6 .2 Hz, 1H), 4.91 (d, J=7.9 Hz, 1H), 4.13 (n, J=7.2 Hz, 1H), 3.97 (d, J=9.8 Hz, 1H), 1.42 (s, 9H), 1.22 (d, J=6.1 Hz, 3H), 0.86 (d, J=7.2 Hz, 3H) 15 ... ... ESIMS m/z 424.5 ([M+H] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 6.73 (d, J=3.4 Hz, 1H), 6.67 (d, J=3.4 Hz, 1H), 6.59-6.46 (m, 2H), 5.43 (dc, J=7.4, 6.2 Hz, 1H), 5.03 (d, J=8.1 Hz, 1H), 4.42 (d, J= 7.3 Hz, 1H), 4.24 (n, J=7.1, 6.7 Hz, 1H), 2.41 (d, J=1.1 Hz, 3H), 2.40 (d, J=1.1Hz, 3H), 1.43(s, 9H), 1.27(d, J=6.2Hz, 3H), 1.09(d, J=7.1Hz, 3H) 16 ... ... ESIMS m/z 412.6 ([M+H] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.18-7.11 (m, 4H), 7.11-7.02 (m, 4H), 5.75 (dc, J=10.2, 6 .2 Hz, 1H), 4.95 (d, J=8.0 Hz, 1H), 4.11 (n, J=7.4, 6.5 Hz, 1H), 3.95 (d, J =10.0 Hz, 1H), 2.27 (s, 3H), 2.25 (s, 3H), 1.41 (s, 9H), 1.22 (d, J=6.1 Hz, 3H ), 0.80 (d, J=7.2 Hz, 3H) 18 ... ... ESIMS m/z 452.6 ([M+H] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.55 (d, J=8.1 Hz, 2H), 7.41 (d, J=8.0 Hz, 2H), 7.31-7.16 (m, 5H), 5.82 (dc, J=9.9, 6.2 Hz, 1H), 4.92 (d, J=7.9 Hz, 1H), 4.15-4.06 ( m, 2H), 1.41 (s, 9H), 1.24 (d, J=6.2 Hz, 3H), 0.77 (d, J=7.2 Hz, 3H)
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -62.58 19 ... ... ESIMS m/z 452.5 ([M+H] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.30-7.22 (m, 4H), 7.22-7.15 (m, 4H), 5.71 (dc, J=9.6, 6 .2 Hz, 1H), 4.91 (d, J=8.0 Hz, 1H), 4.21-4.06 (m, 1H), 4.00 (d, J=9.8 Hz, 1H ), 1.42 (s, 9H), 1.22 (d, J=6.2 Hz, 3H), 0.85 (d, J=7.2 Hz, 3H)
¹³ C NMR (101 MHz, CDCl ₃ ) δ 172.75, 154.96, 139.41, 139.25, 133.03, 132.77, 129.43, 129.35, 129.05, 128.74 , 79.81, 72.51, 56.45, 49.17, 28.30, 19.18, 18.09 20 ... ... ESIMS m/z 406.5 ([M+H] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.25-7.14 (m, 4H), 7.06-6.87 (m, 4H), 5.68 (dc, J=9.3, 6 .2 Hz, 1H), 4.83 (s, 1H), 4.02 (d, J=9.3 Hz, 1H), 3.82 (dd, J=18.2, 5.9 Hz, 1H ), 3.56 (dd, J=18.2, 5.2 Hz, 1H), 1.43 (s, 9H), 1.22 (d, J=6.2 Hz, 3H)
¹³ C NMR (101 MHz, CDCl ₃ ) δ 169.66, 161.74 (d, J=245.9 Hz), 161.63 (d, J=245.7 Hz), 155.45, 136.74 , 129.65 (d, J=7.9 Hz), 115.70 (d, J=21.3 Hz), 115.41 (d, J=21.2 Hz), 79.97, 77.21 , 73.15, 55.84, 42.44, 28.29, 19.17 21 ... ... ESIMS m/z 434.6 ([M+H] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.30-7.15 (m, 4H), 7.06-6.89 (m, 4H), 5.75-5.62 (m, 1H), 4.90 (d, J=8.4 Hz, 1H), 4.11 (q, J=6.7 Hz, 1H), 4.03 (d, J=9.8 Hz, 1H), 1, 49-1.33 (m, 10H), 1.30-1.08 (m, 4H), 0.54 (t, J=7.4 Hz, 3H)
¹³ C NMR (101 MHz, CDCl ₃ ) δ 172.10, 161.70 (d, J=245.6 Hz), 155.20, 136.97, 129.52, 115.71 (d, J=21 .3 Hz), 115.44 (d, J=21.2 Hz), 79.73, 73.12, 56.08, 54.46, 28.30, 25.40, 19.26, 8.95 22 ... ... ESIMS m/z 448.6 ([M+H] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.30-7.15 (m, 4H), 7.04-6.91 (m, 4H), 5.69 (dc, J=9.7.6 .1 Hz, 1H), 4.86 (d, J=9.3 Hz, 1H), 4.09 (dd, J=9.3, 4.2 Hz, 1H), 4.03 (d, J =9.8 Hz, 1H), 1.69-1.57 (m, 1H), 1.42 (s, 9H), 1.21 (d, J=6.2 Hz, 3H), 0.73 (d, J=6.9Hz, 3H), 0.43 (d, J=6.8Hz, 3H)
¹³ C NMR (101 MHz, CDCl ₃ ) δ 171.77, 161.73 (d, J=246.0 Hz), 155.60, 137.05, 129.61, 129.52, 129.44, 115 .71 (d, J=21.6 Hz), 115.49 (d, J=21.4 Hz), 79.69, 73.23, 58.49, 56.03, 30.92, 28.28 , 19.31, 18.96, 16.54 23 ... ... ESIMS m/z 462.7 ([M+H] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.30-7.20 (m, 4H), 7.04-6.92 (m, 4H), 5.68 (dc, J=9.8, 6 .2 Hz, 1H), 4.72 (d, J=8.9 Hz, lH), 4.10 (td, J=9.2, 5.1 Hz, 1H), 4.02 (d, J =10.0 Hz, 1H), 1.41 (s, 9H), 1.22 (d, J=6.1 Hz, 3H), 0.96 (ddd, J=13.7, 9.6, 5.5Hz, 1H), 0.84(m, 1H), 0.75(d, J=6.5Hz, 3H), 0.70(d, J=6.6Hz, 3H)
¹³ C NMR (101 MHz, CDCl ₃ ) δ 173.06, 161.72 (d, J=245.8 Hz), 155.29, 137.17, 136.83, 129.49, 115.73 (d , J=21.4 Hz), 115.46 (d, J=21.3 Hz), 79.74, 73.02, 56.27, 52.04, 41.48, 28.28, 24.41 , 22.76, 21.53, 19.23 24 ... (Thin Film) 3358, 2977, 1708, 1491, 1243, 1162, 1051, 1027 HRMS-ESI (m/z) [M+Na] ⁺ calculated for C ₂₅ H ₃₃ NNaO ₆ , 466.22; found 466.2191 ¹ H NMR (300 MHz, CDCl ₃ ) δ 7.50-7.37 (m, 1H), 7.29-7.19 (m, 1H), 7.20-7.06 (m, 2H), 6.92-6.75 (m, 4H), 5.91 (dc, J=10.1, 6.4 Hz, 1H), 5.03-4.97 (m, 1H), 4.98 ( e, J=9.9 Hz, 1H), 4.22-4.04 (m, 1H), 3.84 (s, 3H), 3.76 (s, 3H), 1.41 (s, 9H ), 1.23 (d, J=6.2 Hz, 3H), 0.82 (d, J=7.2 Hz, 3H) 25 ... (Thin Film) 3368, 2978, 1707, 1597, 1488, 1156, 1043 HRMS-ESI (m/z) [M+Na] ⁺ calculated for C ₂₅ H ₃₃ NNaO ₆ , 466.22; found 466.2193 ¹ H NMR (300 MHz, CDCl ₃ ) δ 7.18 (dt, J=11.8, 7.9 Hz, 2H), 6.89 (dc, J=7.6, 1.5 Hz, 2H) , 6.83 (dt, J=4.0, 2.1 Hz, 2H), 6.71 (dddd, J=10.7, 8.2, 2.6, 0.9 Hz, 2H), 5 .77 (dc, J=10.2, 6.1 Hz, 1H), 4.96 (d, J=8.0 Hz, 1H), 4.20-4.01 (m, 1H), 3, 96 (d, J=10.3 Hz, 1H), 3.77 (s, 3H), 3.75 (s, 3H), 1.42 (s, 9H), 1.24 (d, J=6 .2 Hz, 3H), 0.79 (d, J=7.2 Hz, 3H) 26 ... (Thin Film)3368 2979, 1706, 1504, 1162, 1052 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₅ H ₃₁ F ₂ NNaO ₄ , 470.2113; found 470,2122 ¹ H NMR (300 MHz, CDCl ₃ ) δ 7.14-7.02 (m, 2H), 6.99-6.84 (m, 4H), 5.67 (dc, J=9.8, 6 .2 Hz, 1H), 4.95 (d, J=7.9 Hz, 1H), 4.22-4.05 (m, 1H), 3.94 (d, J=9.8 Hz, 1H ), 2.20 (d, J=2.1 Hz, 3H), 2.19 (d, J=2.2 Hz, 3H), 1.42 (s, 9H), 1.28-1.17 (m, 3H), 0.86 (d, J=7.2 Hz, 3H) 27 ... (Thin Film) 3366, 2978, 1706, 1162, 1051 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₅ H ₃₁ Cl ₂ NNaO ₄ 502.1522; found 502,1533 ¹ H NMR (300 MHz, CDCl ₃ ) δ 7.22 (dd, J=4.6, 1.9 Hz, 2H), 7.13 (t, J=7.9 Hz, 2H), 7.04 (ddd, J=7.6, 5.1, 1.9 Hz, 2H), 5.67 (dc, J=10.0, 6.2 Hz, 1H), 4.96 (d, J=7 .9 Hz, 1H), 4.22-4.05 (m, 1H), 3.91 (d, J=9.9 Hz, 1H), 2.31 (s, 3H), 2.29 (s , 3H), 1.42 (s, 9H), 1.22 (d, J=6.0 Hz, 3H), 0.87 (d, J=7.2 Hz, 3H) 28 ... (Thin Film) 3285, 2979, 2107, 1702, 1501, 1160 HRMS-ESI (m/z) [M+Na] ⁺ calculated for C ₂₇ H ₂₉ NNaO ₄ , 454.1989; found 454,1993 ¹ H NMR (300 MHz, CDCl ₃ ) δ 7.45-7.37 (m, 4H), 7.26-7.18 (m, 4H), 5.75 (dc, J=10.0, 6 .1 Hz, 1H), 4.91 (d, J=7.9 Hz, 1H), 4.20-4.06 (m, 1H), 4.04 (d, J=9.9 Hz, 1H ), 3.05 (s, 1H), 3.04 (s, 1H), 1.42 (s, 9H), 1.23 (d, J=6.2 Hz, 3H), 0.82 (d , J=7.2 Hz, 3H) 29 ... (Thin Film) 3362, 2964, 1712, 1510, 1163, 1053 HRMS-ESI (m/z) [M+Na] ⁺ calculated for C ₂₇ H ₃₇ NNaO ₄ , 462.2615; found 462,2622 ¹ H NMR (300 MHz, CDCl ₃ ) δ 7.22-7.16 (m, 4H), 7.13-7.03 (m, 4H), 5.76 (dc, J=10.2, 6 .1 Hz, 1H), 4.95 (d, J=7.8 Hz, 1H), 4.17-4.02 (m, 1H), 3.96 (d, J=10.2 Hz, 1H ), 2.67-2.45 (m, 4H), 1.41 (s, 9H), 1.23 (d, J=6.2 Hz, 3H), 1.21-1.10 (m, 6H), 0.73 (d, J=7.2 Hz, 3H) 31 ... ... ESIMS m/z 402.6 ([M+H] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.32-7.20 (m, 6H), 7.20-7.14 (m, 1H), 6.97 (t, J=8.7 Hz, 2H), 5.75 (dc, J=10.0, 6.2 Hz, 1H), 4.92 (d, J=8.0 Hz, 1H), 4.11 (t, J=7.4 Hz, 1H), 4.02 (d, J=10.0 Hz, 1H), 1.41 (s, 9H), 1.23 (d, J=6.2 Hz, 3H), 0.77 ( d, J=7.2Hz, 3H)
¹³ C NMR (126 MHz, CDCl ₃ ) δ 172.81, 161.71 (d, J=245.7 Hz), 154.94, 141.23, 137.03 (d, J=3.5 Hz) , 129.56 (d, J=7.9 Hz), 128.59, 127.99, 126.82, 115.62 (d, J=21.3 Hz), 79.70, 72.94, 57 .09, 49.16, 28.31, 14.13 33 ... ... ESIMS m/z 519.6 ([MH ₂ O] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.58 (t, J=2.1 Hz, 2H), 7.38 (dd, J=8.4, 3.9 Hz, 2H), 7.29 -7.25 (m, 1H), 7.20 (dd, J=8.5, 2.2 Hz, 1H), 5.84 (k, J=6.2 Hz, 1H), 4.94 ( e, J=7.8 Hz, 1H), 4.14 (t, J=7.4 Hz, 1H), 3.05 (s, 1H), 1.41 (s, 9H), 1.18 ( d, J=6.3Hz, 3H), 1.00 (d, J=7.2Hz, 3H)
¹³ C NMR (126 MHz, CDCl ₃ ) δ 172.37, 155.04, 144.43, 142.16, 132.90 (d, J=2.7 Hz), 131.93, 131.87, 130 .51, 130.46, 128.13, 127.70, 125.08, 124.99, 80.20, 78.55, 74.10, 49.16, 34.67, 28.25, 14.28 34 ... ... ESIMS m/z 486.5 ([MH ₂ O] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.37-7.28 (m, 4H), 7.18 (ddd, J=8.4, 2.2, 0.8 Hz, 1H), 7, 09 (ddd, J=8.4, 2.2, 0.9 Hz, 1H), 5.86 (c, J=6.2 Hz, 1H), 4.93 (d, J=7.8 Hz , 1H), 4.14 (t, J=7.4 Hz, 1H), 3.06 (s, 1H), 1.41 (s, 9H), 1.18 (d, J=6.3 Hz , 3H), 0.98 (d, J=6.8 Hz, 3H)
¹³ C NMR (126 MHz, CDCl ₃ ) δ 172.28, 158.09 (d, J=249.9 Hz), 158.06 (d, J=249.5 Hz), 155.05, 145.31 (d, J=5.7 Hz), 142.98, 130.64 (d, J=10.0 Hz), 121.90 (d, J=8.8 Hz), 120.38 (d, J =12.3 Hz), 120.24 (d, J=12.3 Hz), 114.59 (d, J=22.6 Hz), 114.20 (d, J=22.9 Hz), 80 .19, 78.60, 74.13, 49.13, 34.67, 28.25, 14.30 35 ... ... ESIMS m/z 480.6 ([M] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.24 (dd, J=10.4, 8.1 Hz, 2H), 7.09 (dd, J=5.5, 2.2 Hz, 2H) , 7.02 (td, J=8.6, 2.3 Hz, 2H), 5.69 (dc, J=10.1, 6.1 Hz, 1H), 4.94 (d, J=7 .9 Hz, 1H), 4.13 (t, J=7.5 Hz, 1H), 3.92 (d, J=10.0 Hz, 1H), 2.33 (s, 3H), 2, 31 (s, 3H), 1.42 (s, 9H), 1.21 (d, J=6.1 Hz, 3H), 0.84 (d, J=7.2 Hz, 3H)
¹³ C NMR (126 MHz, CDCl ₃ ) δ 172.81, 154.92, 139.66, 139.44, 136.53, 136.10, 133.08, 132.72, 130.69, 130.57 , 129.43, 129.12, 126.59, 126.46, 79.77, 72.61, 56.49, 49.17, 28.29, 20.16, 20.09, 19.23, 18 .09 36 ... (Thin Film) 3385, 2980, 1669, 1486, 1452, 1160, 757 … ¹ H NMR (300 MHz, CDCl ₃ ) δ 7.82 (ddd, J=8.6, 7.3, 1.8 Hz, 1H), 7.51 (tt, J=7.9, 1.5 Hz, 1H), 7.33-7.12 (m, 3H), 7.09 (td, J=7.6, 1.4 Hz, 1H), 6.94 (dd, J=8.1, 1.4 Hz, 1H), 6.90 (dd, J=8.1, 1.4 Hz, 1H), 6.23 (cd, J=6.3, 1.6 Hz, 1H), 5, 02 (d, J=7.9 Hz, 1H), 4.30-4.13 (m, 1H), 3.21 (s, 1H), 1.42 (s, 9H), 1.26 (d , J=6.2Hz, 3H), 1.07 (d, J=7.2Hz, 3H) 37 ... (Thin Film) 3375, 2981, 1703, 1609, 1515, 1453, 1433, 1380, 1367, 1284, 1250, 1208, 1162, 1113, 1053, 1023, 967, 909, 873, 821 , 754, 731 HRMS-ESI (m/z) [M+Na] ⁺ calculated for C ₂₃ H ₂₅ F ₄ NNaO ₄ , 478.1612; found 478,1624 ¹ H NMR (300 MHz, CDCl ₃ ) δ 7.18-6.91 (m, 6H), 5.63 (dc, J=9.4, 6.2 Hz, 1H), 4.92 (d, J=8.0 Hz, 1H), 4.24-4.06 (m, 1H), 3.98 (d, J=9.5 Hz, 1H), 1.42 (s, 9H), 1, 23 (d, J=6.1 Hz, 3H), 0.91 (d, J=7.2 Hz, 3H)
¹⁹ F NMR (471 MHz, CDCl ₃ ) δ -136.25 (dt, J=20.6, 9.7 Hz), -136.69 (dt, J=20.4, 9.9 Hz), - 139.30 (dd, J=21.3, 10.5 Hz), -139.70 (dd, J=21.1, 10.1 Hz) 38 ... (Thin Film) 3440, 2981, 1704, 1600, 1497, 1452, 1379, 1367, 1306, 1250, 1210, 1162, 1095, 1054, 1023, 907, 867, 822, 799, 780, 731, 719, 689 HRMS-ESI (m/z) [M+Na] ⁺ calculated for C ₂₃ H ₂₅ Cl ₂ F ₂ NNaO ₄ 510.1021; found 510,1033 ¹ H NMR (300 MHz, CDCl ₃ ) δ 7.32-7.22 (m, 2H), 7.18-7.02 (m, 4H), 5.64 (dc, J=9.6, 6 .2 Hz, 1H), 4.93 (d, J=8.0 Hz, 1H), 4.25-4.03 (m, 1H), 3.98 (d, J=9.6 Hz, 1H ), 1.42 (s, 9H), 1.23 (d, J=6.2 Hz, 3H), 0.92 (d, J=7.2 Hz, 3H)
¹⁹ F NMR (471 MHz, CDCl ₃ ) δ -116.98 (q, J=6.9 Hz), -117.44 (q, J=6.8 Hz) 39 ... (Thin Film) 3364, 2980, 2931, 1707, 1597, 1501, 1451, 1379, 1366, 1307, 1248, 1207, 1163, 1118, 1052, 1023, 959, 908, 881, 821 , 781, 731 HRMS-ESI (m/z) [M+Na] ⁺ calculated for C ₂₅ H ₃₁ F ₂ NNaO ₄ , 470.2113; found 470,2120 ¹ H NMR (300 MHz, CDCl ₃ ) δ 7.13-6.98 (m, 4H), 6.90 (td, J=9.1, 7.4 Hz, 2H), 5.67 (dc, J=10.1, 6.1 Hz, 1H), 4.93 (d, J=8.0 Hz, 1H), 4.22-4.02 (m, 1H), 3.91 (d, J =10.1 Hz, 1H), 2.23 (d, J=2.0 Hz, 3H), 2.21 (d, J=2.0 Hz, 3H), 1.42 (s, 9H), 1.21 (d, J=6.1 Hz, 3H), 0.83 (d, J=7.2 Hz, 3H)
¹⁹ F NMR (471 MHz, CDCl ₃ ) δ -119.99 (q, J=6.8 Hz), -120.57 (q, J=7.0 Hz) 40 ... ... ESIMS m/z 536 ([M+H] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.53 (ddd, J=13.6, 6.7, 4.2 Hz, 8H), 7.45-7.37 (m, 8H), 7, 35-7.29 (m, 2H), 5.87 (dc, J=12.3, 6.1 Hz, 1H), 4.94 (d, J=7.1 Hz, 1H), 4.18 -4.09 (m, 2H), 1.41 (s, 9H), 1.31 (d, J=6.2 Hz, 3H), 0.80 (d, J=7.l Hz, 3H)
¹³ C NMR (126 MHz, CDCl ₃ ) δ 172.93, 154.96, 140.72, 140.60, 140.56, 140.21, 139.92, 139.68, 128.76, 128.75 , 128.51, 127.58, 127.30, 127.27, 127.23, 127.00, 126.96, 79.70, 73.12, 57.33, 49.22, 28.31, 19 .39, 18.04 43 ... ... HRMS-ESI (m/z) [M+Na] ⁺ calculated for C ₂₃ H ₂₅ Cl ₄ NNaO ₄ , 542.0430; found 542.0442 ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.38 (t, J=8.1 Hz, 2H), 7.32 (dd, J=13.6, 2.1 Hz, 2H), 7.10 (dd, J=8.4, 2.1 Hz, 1H), 7.07 (dd, J=8.4, 2.1 Hz, 1H), 5.65 (dc, J=9.5, 6 .2 Hz, 1H), 4.93 (d, J=7.9 Hz, 1H), 4.22-4.09 (m, 1H), 3.97 (d, J=9.5 Hz, 1H ), 1.42 (d, J=0.9 Hz, 9H), 1.24 (d, J=6.1 Hz, 3H), 0.93 (d, J=7.2 Hz, 3H)
¹³ C NMR (126 MHz, CDCl ₃ ) δ 172.73, 154.93, 140.37, 140.26, 133.10, 132.76, 131.66, 131.34, 130.97, 130.67 , 130.23, 130.06, 127.34, 127.27, 79.92, 71.96, 55.79, 49.16, 28.29, 19.14, 18.11 44 ... ... HRMS-ESI (m/z) [M+Na] ⁺ calculated for C ₂₃ H ₂₅ Cl ₂ F ₂ NNaO ₄ 510.1021; found 510,1030 ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.38-7.28 (m, 2H), 7.06 (dd, J=10.0, 1.8 Hz, 1H), 7.04-6, 94 (m, 3H), 5.66 (ddt, J=9.1, 6.9, 5.5 Hz, 1H), 4.92 (d, J=8.0 Hz, 1H), 4.22 -4.08 (m, 1H), 4.01 (d, J=9.4 Hz, 1H), 1.42 (d, J=1.3 Hz, 9H), 1.24 (dd, J= 6.2, 1.3Hz, 3H), 0.92 (d, J=7.2Hz, 3H)
¹³ C NMR (126 MHz, CDCl ₃ ) δ 172.68, 158.17 (d, J=250.1 Hz), 158.03 (d, J=250.1 Hz), 154.93, 141.08 (d, J=6.l Hz), 140.95 (d, J=6.1 Hz), 131.11, 130.80, 124.51 (d, J=3.3 Hz), 124.36 (d, J=3.6 Hz), 120.08 (d, J=17.6 Hz), 119.78 (d, J=17.6 Hz), 116.48 (d, J=16.8 Hz), 116.24, 79.92, 72.02, 56.07, 49.15, 28.28, 19.10, 18.10 45 ... ... ESIMS m/z 300 ([M+H] ⁺ ) ... 46 ... ... ESIMS m/z 284.3 ([M+H] ⁺ ) ... 47 ... ... ESIMS m/z 296.3 ([M+H] ⁺ ) ... 48 ... (Thin Film) 3395, 2885, 1741, 1603, 1508, 1459, 1381, 1324, 1224, 1159, 1137, 1118, 1049, 1015, 955, 881, 826, 793, 779, 755, 746, 721, 693, 666 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₁₈ H ₂₀ F ₂ NO ₂ , 320.1457; found 320,1457 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.55 (s, 3H), 7.22 (dt, J=9.0, 4.8 Hz, 4H), 6.98 (q, J=8, 2 Hz, 4H), 5.71 (dc, J=11.8, 6.1 Hz, 1H), 4.05 (d, J=9.8 Hz, 2H), 1.23 (d, J= 5.9Hz, 3H), 1.13(d, J=6.7Hz, 3H)
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -115.32, -115.70 49 ... ... ESIMS m/z 341.5 ([M+Na] ⁺ ) ... 50 ... ... ESIMS m/z 314.6 ([M+H] ⁺ ) ... 51 ... ... ESIMS m/z 356.4 ([M+H] ⁺ ) ... 52 ... ... ESIMS m/z 302.4 ([M+H] ⁺ ) ¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -169.31 53 ... ... ESIMS m/z 344.5 ([M+H] ⁺ ) ... 54 ... ... ESIMS m/z 320.4 ([M+H] ⁺ ) ... 55 ... ... ESIMS m/z 352.4 ([M+H] ⁺ ) ... 56 ... ... ESIMS m/z 282.4 ([M+H] ⁺ ) ... 57 ... ... ESIMS m/z 298.4 ([M+H] ⁺ ) ... 58 ... ... ESIMS m/z 442.4 ([M+H] ⁺ ) ... 59 ... ... ESIMS m/z 324.4 ([M+H] ⁺ ) ... 60 ... ... ESIMS m/z 312.3 ([M+H] ⁺ ) ... 61 ... ... ESIMS m/z 436 ([M+H] ⁺ ) ... 63 ... ... ESIMS m/z 375.5 ([M+Na] ⁺ ) ... 64 ... ... ESIMS m/z 375.5 ([M+Na] ⁺ ) ... 65 ... ... ESIMS m/z 344.5 ([M+H] ⁺ ) ... 66 ... ... ESIMS m/z 344.5 ([M+H] ⁺ ) ... 67 ... ... ESIMS m/z 348.5 ([M+H] ⁺ ) ... 68 ... ... ESIMS m/z 380.5 ([M+H] ⁺ ) ... 69 ... ... ESIMS m/z 332.5 ([M+H] ⁺ ) ... 70 ... ... ESIMS m/z 340.5 ([M+H] ⁺ ) ... 71 ... (Thin Film) 2959, 1749, 1508, 1401, 1229, 1159, 1055, 830 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₁₇ H ₁₇ F ₂ NO ₂ , 306.1300; found 306,1298 ... 72 ... (Thin Film) 3452, 2855, 1742, 1601, 1506, 1454, 1220, 1159, 1136, 1046, 824 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₁₉ H ₂₂ F ₂ NO ₂ , 335.1646; found 335,1646 ... 73 ... (Thin Film) 2966, 1736, 1602, 1507, 1221, 1158, 1120, 1046, 825 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₀ H ₂₄ F ₂ NO ₂ , 349.1803; found 349,1804 ... 74 ... (Thin Film) 2959, 1739, 1603, 1507, 1219, 1158, 1132, 1046, 825 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₁ H ₂₆ F ₂ NO ₂ , 363.1959; found 363,1959 ... 75 ... (Thin Film) 3411, 2986, 1740, 1605, 1509, 1453, 1223, 1137, 1116, 1049, 700 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₁₈ H ₂₁ FNO ₂ , 302.1551; found 302,1551 ... 77 ... (Thin Film) 3363, 2941, 1743, 1467, 1385, 1236, 1201, 1173, 1136, 1117, 1061, 1029, 992, 824, 755, 723, 675 ESIMS m/z 438.0 ([M+H] ⁺ ) ... 78 ... (Thin Film) 3361, 2942, 1742, 1582, 1486, 1419, 1240, 1207, 1141, 1116, 1057, 800 ESIMS m/z 404.0 ([M] ⁺ ) ... 79 ... (Thin Film) 3218, 2980, 2945, 1742, 1522, 1481, 1245, 1216, 1136, 1118, 1048, 758 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₀ H ₂₄ Cl ₂ NO ₂ , 380.1179; found 380,1181 ... 80 ... ... ESIMS m/z 404.4 ([M+H] ⁺ ) ... 81 ... ... ESIMS m/z 336.5 ([M+H] ⁺ ) ... 83 ... ... ESIMS m/z 408.5 ([M+H] ⁺ ) ... 84 ... (Thin Film) 2881, 2193, 2130, 1742, 1609, 1516, 1457, 1434, 1383, 1325, 1285, 1208, 1118, 1049, 966, 906, 875, 821, 754, 710, 692, 681, 656 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₁₈ H ₁₈ F ₄ NO ₂ , 356.1268; found 356,1273 ¹ H NMR (300 MHz, methanol-d ₄ ) δ 7.46-7.30 (m, 2H), 7.28-7.14 (m, 4H), 5.84 (dc, J=10.1 , 6.2 Hz, 1H), 4.24 (d, J=10.1 Hz, 1H), 3.96 (c, J=7.3 Hz, 1H), 3.31 (pd, J=1 .6, 0.5 Hz, 3H), 1.27 (d, J=6.1 Hz, 3H), 1.02 (d, J=7.2 Hz, 3H)
¹⁹ F NMR (471 MHz, methanol-d ₄ ) δ -139.39 (ddd, J=19.8, 11.5, 7.5 Hz), -139.57 - -139.84 (m), - 142.33 - -142.56 (m), -142.66 - -142.93 (m) 85 ... (Thin Film) 3409, 2928, 2026, 1957, 1743, 1597, 1499, 1458, 1408, 1323, 1249, 1208, 1118, 1061, 917, 866, 822, 798, 780, 753, 718, 690, 663 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₁₈ H ₁₈ Cl ₂ F ₂ NO ₂ , 388.0677; found 388.0677 ¹ H NMR (300 MHz, methanol-d ₄ ) δ 7.54 (dt, J=7.0, 2.7 Hz, 2H), 7.37 (ddt, J=8.6, 4.3, 2 .1 Hz, 2H), 7.21 (td, J=8.8, 4.7 Hz, 2H), 5.93-5.75 (m, 1H), 4.24 (d, J=10, 1 Hz, 1H), 3.96 (q, J=7.3 Hz, 1H), 3.31 (t, J=1.7 Hz, 3H), 1.28 (d, J=6.1 Hz , 3H), 1.03 (d, J=7.3 Hz, 3H)
¹⁹ F NMR (471 MHz, methanol-d ₄ ) δ -119.62 - -119.72 (m), -119.99 - -120.08 (m) 86 ... (Thin Film) 3374, 2928, 1742, 1596, 1501, 1457, 1379, 1323, 1233, 1206, 1118, 1052, 1003, 956, 933, 886, 824, 780, 752, 721, 7 11, 690, 681, 671, 664, 655 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₀ H ₂₄ F ₂ NO ₂ , 348.1770; found 348,1771 ¹ H NMR (300 MHz, methanol-d ₄ ) δ 7.30-7.12 (m, 4H), 6.95 (td, J=8.9, 6.6 Hz, 2H), 5.91- 5.74 (m, 1H), 4.07 (d, J=10.4 Hz, 1H), 3.99-3.83 (m, 1H), 3.30 (dtd, J=3.3, 1.6, 0.6 Hz, 3H), 2.23 (t, J=2.6 Hz, 6H), 1.25 (d, J=6.1 Hz, 3H), 0.94 (dd, J=7.3, 0.7Hz, 3H)
¹⁹ F NMR (471 MHz, methanol-d ₄ ) δ -122.00 - -122.37 (m), -122.69 (tt, J=6.1, 2.9 Hz) 87 ... (Thin Film) 2879, 1746, 1587, 1561, 1517, 1468, 1395, 1227, 1194, 1116, 1053, 1029, 871, 822, 747, 727, 669 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₁₈ H ₁₈ C ₁₄ NO ₂ , 420.0086; found 420,0090 ... 88 ... (Thin Film) 2858, 1747, 1580, 1486, 1458, 1383, 1368, 1278, 1236, 1206, 1119, 1048, 970, 871, 824, 779, 761, 682 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₁₈ H ₁₈ C ₁₂ F ₂ NO ₂ , 388.0677; found 388.0688 ... 89 ... ... HRMS-ESI (m/z) [M] ⁺ calculated for C ₂₅ H ₂₆ N ₂ O ₆ , 450.1791; found 450,1794 ¹ H NMR (500 MHz, CDCl ₃ ) δ 11.97 (d, J=0.5 Hz, 1H), 8.33 (d, J=8.1 Hz, 1H), 7.96 (d, J =5.2 Hz, 1H), 7.47 (ddt, J=8.5, 6.4, 1.3 Hz, 4H), 7.33-7.13 (m, 5H), 6.89- 6.81(m, 1H), 6.03(k, J=6.3Hz, 1H), 4.62-4.49(m, 1H), 3.93(s, 3H), 2.74 (s, 1H), 1.23 (d, J=6.3 Hz, 3H), 1.07 (d, J=7.2 Hz, 3H)
¹³ C NMR (126 MHz, CDCl ₃ ) δ 171.30, 168.61, 155.37, 148.71, 144.85, 142.71, 140.44, 130.29, 128.33, 128.32 , 127.22, 127.16, 125.51, 125.45, 109.44, 79.57, 75.54, 56.08, 47.85, 17.62, 14.32 90 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₅ H ₂₇ N ₂ O ₅ , 435.1920; found 435,1925 ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.10 (d, J=0.6 Hz, 1H), 8.34 (d, J=8.0 Hz, 1H), 7.98 (d, J =5.2 Hz, 1H), 7.38-7.06 (m, 10H), 6.86 (dd, J=5.3, 0.7 Hz, 1H), 5.83 (dc, J= 10.1, 6.1 Hz, 1H), 4.52 (dc, J=8.1, 7.2 Hz, 1H), 4.06 (d, J=10.2 Hz, 1H), 3, 93 (s, 3H), 1.26 (d, J=6.1 Hz, 3H), 0.97 (d, J=7.2 Hz, 3H)
¹³ C NMR (101 MHz, CDCl ₃ ) δ 171.67, 168.53, 155.34, 148.72, 141.38, 141.13, 140.40, 130.48, 128.80, 128.50 , 128.10, 128.03, 126.95, 126.70, 109.39, 73.57, 57.93, 56.07, 47.85, 19.24, 17.61 91 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₁ H ₂₃ N ₂ O ₅ S ₂ , 447.1048; found 447,1047 ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.10 (d, J=0.6 Hz, 1H), 8.41 (d, J=8.0 Hz, 1H), 7.98 (d, J =5.2 Hz, 1H), 7.18-7.16 (m, 2H), 7.01 (ddd, J=3.6, 1.3, 0.6 Hz, 1H), 6.94- 6.88 (m, 3H), 6.86 (dd, J=5.3, 0.7 Hz, 1H), 5.56 (dc, J=7.4, 6.2 Hz, 1H), 4 .70-4.58 (m, 2H), 3.94 (s, 3H), 1.30 (d, J=6.2 Hz, 3H), 1.24 (d, J=1.2 Hz, 3H)
¹³ C NMR (101 MHz, CDCl ₃ ) δ 171.48, 168.62, 155.35, 148.74, 143.75, 142.69, 140.43, 130.48, 126.77, 126.57 , 126.05, 125.43, 124.61, 124.58, 109.44, 74.83, 56.08, 47.98, 47.42, 18.69, 17.80 92 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₅ H ₂₅ F ₂ N ₂ O ₅ , 471.1731; found 471,1735 ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.06 (d, J=0.7 Hz, 1H), 8.32 (d, J=8.0 Hz, 1H), 7.98 (d, J =5.3 Hz, 1H), 7.26-7.18 (m, 4H), 7.01-6.89 (m, 4H), 6.87 (d, J=5.3 Hz, 1H) , 5.73 (dc, J=9.7, 6.1 Hz, 1H), 4.59 _ 4.49 (m, 1H), 4.05 (d, J=9.8 Hz, 1H), 3.94 (s, 3H), 1.25 (d, J=6.2 Hz, 3H), 1.07 (d, J=7.2 Hz, 3H)
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -115.46, -115.80 93 ... ... HRMS-ESI (m/z) [2M+Na] ⁺ calculated for C ₅₄ H ₆₀ N ₄ NaO ₁₂ , 979.4106; found 979.4119 ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.03 (d, J=0.7 Hz, 1H), 8.40 (d, J=8.1 Hz, 1H), 7.97 (d, J =5.2Hz, 1H), 7.41-7.09(m, 10H), 6.85(d, J=5.2Hz, 1H), 5.97(k, J=6.3Hz , 1H), 4.61 (dc, J=8.2, 7.2 Hz, 1H), 3.94 (s, 3H), 3.39 (dc, J=9.1, 6.9 Hz, 1H), 3.18 (dc, J=9.2, 6.9 Hz, 1H), 1.30 (d, J=7.2 Hz, 3H), 1.17 (t, J=6.9 Hz, 3H), 1.13 (d, J=6.3 Hz, 3H)
¹³ C NMR (101 MHz, CDCl ₃ ) δ 171.45, 168.56, 155.34, 148.71, 141.84, 140.56, 140.38, 130.37, 128.25, 127.87 , 127.81, 127.69, 127.33, 127.21, 109.41, 84.05, 74.30, 59.93, 56.08, 48.05, 18.02, 15.67, 14 .95 95 ... ... HRMS-ESI (m/z) [M-OCH ₃ ]+ calculated for C ₂₅ H ₂₅ N ₂ O ₅ , 433.1764; found 433,1763 ¹ H NMR (300 MHz, CDCl ₃ ) δ 12.04 (d, J=0.6 Hz, 1H), 8.41 (d, J=8.0 Hz, 1H), 7.97 (d, J =5.2Hz, 1H), 7.41-7.18(m, 10H), 6.85(d, J=5.4Hz, 1H), 5.97(k, J=6.3Hz , 1H), 4.75-4.49 (m, 1H), 3.94 (s, 3H), 3.15 (s, 3H), 1.29 (d, J=7.2 Hz, 3H) , 1.13 (d, J=6.3 Hz, 3H)
¹³ C NMR (101 MHz, CDCl ₃ ) δ 171.42, 168.58, 155.35, 148.72, 141.11, 140.39, 139.89, 130.37, 128.51, 128.11 , 127.86, 127.69, 127.52, 127.31, 109.42, 84.47, 74.02, 56.08, 52.55, 48.05, 17.97, 14.97 96 ... ... ... ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.03 (d, J=0.6 Hz, 1H), 8.31 (d, J=7.9 Hz, 1H), 7.97 (d, J =5.2 Hz, 1H), 7.35 (td, J=8.5, 6.2 Hz, 1H), 7.23 (td, J=8.4, 6.2 Hz, 1H), 6 .91-6.74 (m, 4H), 6.69 (ddd, J=10.4, 8.8, 2.6 Hz, 1H), 5.88-5.74 (m, 1H), 4 .69 (d, J=9.9 Hz, 1H), 4.64-4.48 (m, 1H), 3.95 (s, 3H), 1.30 (d, J=6.1 Hz, 3H), 1.17 (d, J=7.2 Hz, 3H)
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -110.97 (d, J=7.7 Hz), -111.39 (d, J=7.6 Hz), -111.98 (dd, J= 7.7, 2.6Hz), -112.83 (dd, J=7.6, 2.6Hz) 97 ... ... ... ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.06 (s, 1H), 8.31 (d, J=7.9 Hz, 1H), 7.98 (d, J=5.2 Hz, 1H ), 7.49-7.40 (m, 4H), 7.37-7.24 (m, 5H), 7.23-7.18 (m, 1H), 6.86 (d, J=5 .2 Hz, 1H), 6.00 (dc, J=25.4, 6.4 Hz, 1H), 4.63-4.51 (m, 1H), 3.94 (s, 3H), 1 .32 (dd, J=6.5, 1.0 Hz, 3H), 0.96 (d, J=7.2 Hz, 3H)
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -169.17 98 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₇ H ₃₁ N ₂ O ₇ , 495.2131; found 495,2124 ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.11 (s, 1H), 8.35 (d, J=8.0 Hz, 1H), 7.97 (d, J=5.2 Hz, 1H ), 7.22-7.12 (m, 4H), 6.90-6.73 (m, 5H), 5.73 (dc, J=9.8, 6.1 Hz, 1H), 4, 64-4.44 (m, 1H), 3.96 (d, J=9.9 Hz, 1H), 3.93 (s, 3H), 3.75 (s, 3H), 3.73 (s , 3H), 1.24 (d, J=6.2 Hz, 3H), 1.05 (d, J=7.2 Hz, 3H)
¹³ C NMR (101 MHz, CDCl ₃ ) δ 171.65, 168.54, 158.36, 158.20, 155.34, 148.70, 140.40, 133.83, 133.69, 130.45 , 128.97, 128.92, 114.11, 113.81, 109.39, 73.77, 56.11, 56.04, 55.20, 55.19, 47.90, 19.20, 17 .75 99 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₅ H ₂₅ F ₂ N ₂ O ₅ , 471.1731; found 471,1724 ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.05 (s, 1H), 8.34 (d, J=8.0 Hz, 1H), 7.98 (d, J=5.3 Hz, 1H ), 7.32-7.19 (m, 2H), 7.11-7.03 (m, 2H), 7.02-6.83 (m, 5H), 5.75 (dc, J=9 .8, 6.1 Hz, 1H), 4.65-4.46 (m, 1H), 4.06 (d, J=9.9 Hz, 1H), 3.94 (s, 3H), 1 .27 (d, J=6.1 Hz, 3H), 1.07 (d, J=7.2 Hz, 3H)
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -112.07, -112.48 100 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₅ H ₂₅ Cl ₂ N ₂ O ₅ , 503.1140; found 503,1137 ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.04 (s, 1H), 8.32 (d, J=7.7 Hz, 1H), 7.98 (d, J=5.3 Hz, 1H ), 7.31-7.10 (m, 8H), 6.86 (d, J=5.2 Hz, 1H), 5.73 (dc, J=9.9, 6.2 Hz, 1H) , 4.60-4.48 (m, 1H), 4.01 (d, J=10.0 Hz, 1H), 3.94 (s, 3H), 1.27 (d, J=6.2 Hz, 3H), 1.08 (d, J=7.1 Hz, 3H)
¹³ C NMR (101 MHz, CDCl ₃ ) δ 171.55, 168.60, 155.36, 148.72, 142.54, 142.33, 140.47, 134.73, 134.42, 130.33 , 130.23, 129.94, 128.42, 128.33, 127.52, 127.21, 126.18, 125.98, 109.47, 72.83, 57.03, 56.08, 47 .85, 19.11, 17.66 101 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₅ H ₂₅ N ₂ O ₅ , 433.1763; found 433,1749 ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.23-11.94 (m, 1H), 8.64-8.39 (m, 1H), 8.11-7.92 (m, 1H), 7.78-7.60(m, 3H), 7.59-7.48(m, 1H), 7.46-7.35(m, 2H), 7.36-7.26(m, 1H ), 7.27-7.20 (m, 1H), 6.91-6.84 (m, 1H), 5.87-5.69 (m, 1H), 4.94-4.76 (m , 1H), 4.35-4.22 (m, 1H), 4.00-3.93 (m, 3H), 1.69-1.51 (m, 3H), 0.95 -0.59 (m, 3H) 102 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₅ H ₂₅ N ₂ O ₆ , 449.1712; found 449,1707 ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.16 (s, 1H), 8.51-8.38 (m, 1H), 8.11-7.82 (m, 1H), 7.34- 7.15 (m, 4H), 7.15-6.94 (m, 4H), 6.91-6.77 (m, 1H), 5.20-5.09 (m, 1H), 4. 78-4.64 (m, 1H), 4.33-4.17 (m, 1H), 3.96-9.92 (m, 3H), 1.55-1.42 (m, 3H), 1.10-0.91 (m, 3H) 103 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₅ H ₂₅ Br ₂ N ₂ O ₅ , 591.0130; found 591.0125 ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.06 (s, 1H), 8.33 (d, J=7.9 Hz, 1H), 7.97 (d, J=5.2 Hz, 1H ), 7.50-7.31 (m, 4H), 7.24-7.01 (m, 4H), 6.87 (d, J=5.2 Hz, 1H), 5.73 (dc, J=9.6, 6.1 Hz, 1H), 4.55 (p, J=7.3 Hz, 1H), 4.01 (d, J=9.7 Hz, 1H), 3.93 ( s, 3H), 1.25 (d, J=6.1 Hz, 3H), 1.09 (d, J=7.2 Hz, 3H)
¹³ C NMR (101 MHz, CDCl ₃ ) δ 171.50, 168.61, 155.39, 148.74, 140.47, 139.69, 139.59, 132.00, 131.69, 130.31 , 129.80, 129.73, 121.12, 120.84, 109.52, 72.81, 56.45, 56.08, 47.86, 19.09, 17.67 104 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₃ H ₂₇ N ₂ O ₅ S ₂ , 475.1361; found 475,1368 ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.13 (s, 1H), 8.44 (d, J=8.0 Hz, 1H), 7.99 (d, J=5.2 Hz, 1H ), 6.87 (d, J=5.2 Hz, 1H), 6.73 (d, J=3.4 Hz, 1H), 6.67 (d, J=3.4 Hz, 1H), 6.54-6.35 (m, 2H), 5.54-5.40 (m, 1H), 4.78-4.59 (m, 1H), 4.45 (d, J=7.1 Hz, 1H), 3.94 (s, 3H), 2.39 (s, 6H), 1.30 (d, J=2.8 Hz, 3H), 1.28 (d, J=3.7 Hz, 3H)
¹³ C NMR (101 MHz, CDCl ₃ ) δ 171.50, 168.60, 155.35, 148.74, 141.52, 140.47, 140.41, 139.03, 139.00, 130.53 , 125.76, 125.08, 124.67, 124.42, 109.41, 74.68, 56.07, 48.00, 47.84, 18.65, 17.88, 15.25 105 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₇ H ₃₁ N ₂ O ₅ , 463.2233; found 463,2242 ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.14 (s, 1H), 8.38 (d, J=8.0 Hz, 1H), 7.94 (d, J=5.2 Hz, 1H ), 7.21-7.10 (m, 4H), 7.09-6.97 (m, 4H), 6.82 (d, J=5.2 Hz, 1H), 5.79 (dc, J=10.1, 6.2 Hz, 1H), 4.53 (p, J=7.3 Hz, 1H), 3.98 (d, J=10.0 Hz, 1H), 3.88 ( s, 3H), 2.25 (s, 3H), 2.23 (s, 3H), 1.25 (d, J=6.3 Hz, 3H), 1.01 (d, J=7.2 Hz, 3H)
¹³ C NMR (101 MHz, CDCl ₃ ) δ 171.66, 168.57, 155.32, 148.71, 140.43, 138.63, 138.47, 136.37, 136.05, 130.45 , 129.44, 129.11, 127.91, 127.85, 109.45, 73.66, 57.08, 56.02, 47.92, 20.97, 20.93, 19.24, 17 .64 106 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₆ H ₂₆ F ₃ N ₂ O ₅ , 503.1794; found 503,1794 ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.09 (s, 1H), 8.35 (d, J=8.0 Hz, 1H), 7.97 (d, J=5.2 Hz, 1H ), 7.54 (d, J=8.1 Hz, 2H), 7.42 (d, J=8.1 Hz, 2H), 7.34-7.21 (m, 4H), 7.21 -7.13 (m, 1H), 6.86 (d, J=5.2 Hz, 1H), 5.85 (dc, J=9.8, 6.1 Hz, 1H), 4.61- 4.46 (m, 1H), 4.15 (d, J=9.9 Hz, 1H), 3.93 (s, 3H), 1.27 (d, J=6.2 Hz, 3H), 1.00 (d, J=7.2Hz, 3H)
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -62.53 107 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₅ H ₂₅ Cl ₂ N ₂ O ₅ , 503.1140; found 503,1139 ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.05 (s, 1H), 8.32 (d, J=8.0 Hz, 1H), 7.97 (d, J=5.2 Hz, 1H ), 7.38-7.10 (m, 8H), 6.87 (d, J=5.2 Hz, 1H), 5.73 (dc, J=9.9, 6.2 Hz, 1H) , 4.62-4.45 (m, 1H), 4.03 (d, J=9.6 Hz, 1H), 3.94 (s, 3H), 1.25 (d, J=6.1 Hz, 3H), 1.09 (d, J=7.2 Hz, 3H)
¹³ C NMR (101 MHz, CDCl ₃ ) δ 171.52, 168.61, 155.41, 148.74, 140.45, 139.26, 139.15, 133.04, 132.77, 130.32 , 129.41, 129.36, 129.05, 128.73, 109.49, 72.95, 56.35, 56.08, 47.86, 19.08, 17.67 109 ... ... ESIMS m/z 587 ([M+H] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.10 (s, 1H), 8.36 (d, J=7.9 Hz, 1H), 7.95 (d, J=5.2 Hz, 1H ), 7.57-7.46 (m, 8H), 7.43-7.38 (m, 7H), 7.34-7.29 (m, 2H), 6.81 (d, J=5 .2 Hz, 1H), 5.90 (dc, J=12.2, 6.1 Hz, 1H), 4.56 (n, J=7.2 Hz, 1H), 4.16 (d, J =10.0 Hz, 1H), 3.89 (d, J=1.9 Hz, 3H), 1.34 (d, J=6.1 Hz, 3H), 1.02 (d, J=7 .2 Hz, 3H)
¹³ C NMR (101 MHz, CDCl ₃ ) δ 171.71, 168.59, 155.33, 148.72, 140.65, 140.58, 140.43, 140.11, 139.94, 139.66 130.44, 128.77, 128.73, 128.67, 128.53, 127.58, 127.30, 127.26, 127.21, 127.00, 126.94, 109.40, 73 .58, 57.25, 56.04, 47.91, 19.33, 17.66 110 ... (Thin Film) 3374, 2984, 1735, 1649, 1602, 1577, 1530, 1507, 1449, 1380, 1329, 1296, 1222, 1188, 1159, 1130, 1105, 1049, 1015, 906, 826, 809, 792, 778, 731, 704, 666 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₄ H ₂₃ F ₂ N ₂ O ₄ , 441.1620; found 441,1620 ¹ H NMR (400 MHz, CDCl ₃ ) δ 11.80 (s, 1H), 8.30 (d, J=8.0 Hz, 1H), 8.07 (dd, J=4.3, 1, 5 Hz, 1H), 7.40-7.15 (m, 6H), 7.05-6.85 (m, 4H), 5.73 (dc, J=9.8, 6.2 Hz, 1H ), 4.65-4.45 (m, 1H), 4.05 (d, J=9.8 Hz, 1H), 1.25 (d, J=6.1 Hz, 3H), 1.07 (d, J=7.2Hz, 3H)
¹³ C NMR (101 MHz, CDCl ₃ ) δ 171.60, 168.26, 161.76 (d, J=246.1 Hz), 161.64 (d, J=245.7 Hz), 157.79 , 139.65, 136.82 (d, J=3.3 Hz), 136.71 (d, J=3.5 Hz), 131.04, 129.50 (d, J=7.9 Hz) , 128.80, 126.08, 115.74 (d, J=21.3 Hz), 115.41 (d, J=21.3 Hz), 73.34, 56.14, 47.84, 19 .12, 17.69
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -115.44, -115.76 111 ... (Thin Film) 3370, 2984, 2936, 2256, 1735, 1647, 1604, 1574, 1529, 1507, 1483, 1469, 1452, 1381, 1323, 1281, 1262, 1222, 1158, 1109, 1048, 1015, 990, 904, 824, 800, 730 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₆ H ₂₇ F ₂ N ₂ O ₅ , 485.1883; found 485,1880 ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.06 (d, J=0.6 Hz, 1H), 8.33 (d, J=8.0 Hz, 1H), 7.95 (d, J =5.2 Hz, 1H), 7.35-7.14 (m, 4H), 7.04-6.87 (m, 4H), 6.84 (d, J=5.2 Hz, 1H) , 5.73 (dc, J=9.7, 6.1 Hz, 1H), 4.60-4.48 (m, 1H), 4.16 (q, J=7.0 Hz, 2H), 4.05 (d, J=9.7 Hz, 1H), 1.51 (t, J=7.0 Hz, 3H), 1.24 (d, J=6.1 Hz, 3H), 1, 06 (d, J=7.2Hz, 3H)
¹³ C NMR (101 MHz, CDCl ₃ ) δ 171.58, 168.66, 161.75 (d, J=246.1 Hz), 161.64 (d, J=245.7 Hz), 154.75 , 148.82, 140.38, 136.82 (d, J=3.3 Hz), 136.73 (d, J=3.3 Hz), 130.41, 129.51 (d, J=7 .6 Hz), 115.72 (d, J=21.4 Hz), 115.39 (d, J=21.2 Hz), 110.13, 73.32, 64.67, 56.12, 47 .84, 19.11, 17.69, 14.37
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -115.47, -115.80 112 ... (Thin Film) 3370, 2984, 1729, 1641, 1601, 1531, 1507, 1491, 1450, 1361, 1305, 1281, 1254, 1222, 1177, 1158, 1135, 1087, 1048, 1015, 908, 824, 778, 752, 731, 666 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₅ H ₂₄ F ₂ NO ₄ , 440.1668; found 440,1676 ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.05 (s, 1H), 7.43-7.33 (m, 2H), 7.30-7.17 (m, 4H), 7.05- 6.90 (m, 5H), 6.88-6.77 (m, 2H), 5.75 (dc, J=9.9, 6.1 Hz, 1H), 4.57 (n, J= 7.1 Hz, 1H), 4.06 (d, J=9.9 Hz, 1H), 1.25 (d, J=6.1 Hz, 3H), 1.00 (d, J=7, 1Hz, 3H)
¹³ C NMR (101 MHz, CDCl ₃ ) δ 172.22, 169.33, 161.79 (d, J=246.2 Hz), 161.70 (d, J=245.9 Hz), 161.59 , 136.83 (d, J=3.4 Hz), 136.61 (d, J=3.4 Hz), 134.49, 129.49 (d, J=8.1 Hz), 129.46 (d, J=7.9 Hz), 125.62, 118.70, 118.58, 115.79 (d, J=21.4 Hz), 115.50 (d, J=21.3 Hz) , 113.72, 73.62, 56.17, 48.29, 19.15, 17.79
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -115.30, -115.60 113 ... ... ESIMS m/z 457.6 ([M+H] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 11.98 (d, J=0.6 Hz, 1H), 8.30 (t, J=5.7 Hz, 1H), 7.99 (d, J =5.2 Hz, 1H), 7.24-7.15 (m, 4H), 7.03-6.85 (m, 5H), 5.71 (dc, J=9.2, 6.2 Hz, 1H), 4.11 (dd, J=18.1, 6.0 Hz, 1H), 4.04 (d, J=9.2 Hz, 1H), 3.95 (s, 3H), 3.90 (dd, J=18.1, 5.6 Hz, 1H), 1.25 (d, J=6.3 Hz, 3H)
¹³ C NMR (101 MHz, CDCl ₃ ) δ 169.18, 168.43, 161.74 (d, J=246.1 Hz), 161.63 (d, J=245.5 Hz), 155.42 , 148.71, 140.55, 136.68, 130.30, 129.68, 129.60, 115.67 (d, J=29.2 Hz), 115.46 (d, J=29.1 Hz), 109.55, 73.65, 56.11, 55.77, 40.91, 19.12 114 ... ... ESIMS m/z 485.6 ([M+H] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.08 (s, 1H), 8.32 (d, J=8.5 Hz, 1H), 7.98 (d, J=5.2 Hz, 1H ), 7.46-7.04 (m, 4H), 7.11-6.65 (m, 5H), 5.71 (dc, J=9.8, 6.2 Hz, 1H), 4, 51 (ddd, J=8.5, 7.0, 5.4 Hz, 1H), 4.05 (d, J=9.6 Hz, 1H), 3.95 (s, 3H), 1.70 -1.57 (m, 1H), 1.49-1.36 (m, 1H), 1.24 (d, J=6.2 Hz, 3H), 0.67 (t, J=7.5 Hz, 3H)
¹³ C NMR (101 MHz, CDCl ₃ ) δ 170.87, 168.79, 161.74 (d, J=245.9 Hz), 161.66 (d, J=245.8 Hz), 155.43 , 148.73, 140.42, 136.80, 130.36, 129.55 (d, J=2.1 Hz), 129.47 (d, J=2.1 Hz), 115.67 (d , J=32.4 Hz), 115.45 (d, J=32.4 Hz), 109.44, 73.48, 56.09, 56.03, 53.16, 25.16, 19.18 , 9.27 115 ... ... ESIMS m/z 499.6 ([M+H] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.08 (d, J=0.6 Hz, 1H), 8.32 (d, J=9.4 Hz, 1H), 7.98 (d, J =5.2Hz, 1H), 7.31-7.07(m, 4H), 6.97(t, J=8.6Hz, 2H), 6.93-6.86(m, 3H) , 5.72 (dc, J=9.7, 6.2 Hz, 1H), 4.48 (dd, J=9.4, 4.7 Hz, 1H), 4.05 (d, J=9 .1 Hz, 1H), 3.95 (s, 3H), 1.93-1.82 (m, 1H), 1.23 (d, J=6.1 Hz, 3H), 0.82 (d , J=6.9Hz, 3H), 0.65 (d, J=6.8Hz, 3H)
¹³ C NMR (101 MHz, CDCl ₃ ) δ 170.46, 168.95, 161.73 (d, J=246.4 Hz), 161.65 (d, J=245.6 Hz), 155.43 , 148.71, 140.42, 136.85, 130.40, 129.54 (d, J=4.7 Hz), 129.47 (d, J=4.7 Hz), 115.71 (d , J=21.3 Hz), 115.40 (d, J=21.3 Hz), 109.43, 73.51, 57.09, 56.09, 55.98, 30.96, 19.22 , 19.10, 17.10 116 ... ... ESIMS m/z 513.7 ([M+H] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.07 (d, J=0.6 Hz, 1H), 8.15 (d, J=8.9 Hz, 1H), 7.97 (d, J =5.2 Hz, 1H), 7.31-7.04 (m, 4H), 7.08-6.74 (m, 6H), 5.70 (dc, J=10.0, 6.1 Hz, 1H), 4.54 (ddd, J=9.7, 8.8, 5.0 Hz, 1H), 4.04 (d, J=9.8 Hz, 1H), 3.94 (s , 3H), 1.46-1.36 (m, 1H), 1.33-1.18 (m, 4H), 1.08 (ddd, J=13.9, 9.0, 5.0 Hz , 1H), 0.82 (d, J=6.5 Hz, 3H), 0.77 (d, J=6.6 Hz, 3H)
¹³ C NMR (101 MHz, CDCl ₃ ) δ 171.62, 168.81, 161.75 (d, J=246.2 Hz), 161.66 (d, J=245.6 Hz), 155.43 , 148.74, 140.39, 137.02, 136.76, 130.34, 129.51 (d, J=3.4 Hz), 129.44 (d, J=3.5 Hz), 115 .73 (d, J=21.4 Hz), 115.41 (d, J=21.3 Hz), 109.44, 73.37, 56.21, 56.09, 50.52, 41.00 , 24.57, 22.76, 21.49, 19.14 117 ... (Thin Film) 3368, 2937, 1732, 1648, 1527, 1241, 1144 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₇ H ₃₁ N ₂ O ₇ , 495.2126; found 495,2104 ¹ H NMR (300 MHz, CDCl ₃ ) δ 12.15 (d, J=0.6 Hz, 1H), 8.38 (d, J=8.0 Hz, 1H), 7.97 (d, J =5.2Hz, 1H), 7.45(dd, J=7.6, 1.7Hz, 1H), 7.30-7.20(m, 1H), 7.12(dddd, J= 13.5, 8.1, 7.5, 1.7 Hz, 2H), 6.92-6.80 (m, 4H), 6.76 (dd, J=8.2, 1.1 Hz, 1H), 5.97 (dc, J=9.0, 5.7, 5.2 Hz, 1H), 5.01 (d, J=10.1 Hz, 1H), 4.70-4.39 (m, 1H), 3.93 (s, 3H), 3.85 (s, 3H), 3.75 (s, 3H), 1.25 (d, J=6.2 Hz, 3H), 1 .01 (d, J=7.2 Hz, 3H) 118 ... (Thin Film) 3368, 2937, 1734, 1648, 1527, 1261, 1148, 1041 HRMS-ESI (m/z) ([M+H] ⁺ ) calcd C ₂₇ H ₃₁ N ₂ O ₇ , 495.2126; found 495,2106 ¹ H NMR (300 MHz, CDCl ₃ ) δ 12.10 (d, J=0.6 Hz, 1H), 8.35 (d, J=8.0 Hz, 1H), 7.98 (d, J =5.2Hz, 1H), 7.21(t,.7=8.0Hz, 1H), 7.15(t, J=7.9Hz, 1H), 6.93-6.81( m, 5H), 6.74 (ddd, J=8.2, 2.6, 0.9 Hz, 1H), 6.68 (ddd, J=8.2, 2.6, 0.9 Hz, 1H), 5.80 (dc, J=10.3, 6.1 Hz, 1H), 4.60-4.43 (m, 1H), 3.99 (d, J=10.3 Hz, 1H ), 3.94 (s, 3H), 3.77 (s, 3H), 3.75 (s, 3H), 1.26 (d, J=6.0 Hz, 3H), 1.00 (d , J=7.2 Hz, 3H) 119 ... (Thin Film) 3367, 2985, 1738, 1647, 1575, 1481, 1263, 1153, 1058, 914 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₅ H ₂₃ Cl ₂ F ₂ N ₂ O ₆ , 555.0896; found 555,0909 ¹ H NMR (300 MHz, CDCl ₃ ) δ 11.92 (s, 1H), 8.36 (d, J=8.1 Hz, 1H), 7.95 (d, J=5.2 Hz, 1H ), 7.77 (t, J=8.5 Hz, 1H), 7.37 (t, J=8.5 Hz, 1H), 7.15 (ddd, J=8.5, 2.1, 0.7 Hz, 1H), 7.08-6.89 (m, 3H), 6.86 (d, J=5.3 Hz, 1H), 6.10 (q, J=6.2 Hz, 1H), 4.66 (n, J=7.3 Hz, 1H), 3.95 (s, 3H), 3.22 (s, 1H), 1.36 (d, J=7.2 Hz, 3H), 1.24 (d, J=6.3 Hz, 3H) 120 ... (Thin Film) 3369, 2934, 1735, 1648, 1576, 1527, 1451, 1261 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₇ H ₂₉ F ₂ N ₂ O ₅ , 499.2039; found 499,2050 ¹ H NMR (300 MHz, CDCl ₃ ) δ 12.06 (d, J=0.6 Hz, 1H), 8.34 (d, J=8.0 Hz, 1H), 7.98 (d, J =5.2 Hz, 1H), 7.16-7.01 (m, 2H), 7.01-6.79 (m, 5H), 5.70 (dc, J=9.9, 6.1 Hz, 1H), 4.70-4.43 (m, 1H), 3.97 (d, J=9.3 Hz, 1H), 3.94 (s, 3H), 2.20 (d, J =1.9 Hz, 3H), 2.17 (d, J=1.9 Hz, 3H), 1.25 (d, J=6.1 Hz, 3H), 1.09 (d, J=7 .2 Hz, 3H) 121 ... (Thin Film) 3367, 2980, 1735, 1648, 1527, 1450, 1262, 1050 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₇ H ₂₉ Cl ₂ N ₂ O ₅ , 531.1448; found 531,1458 ¹ H NMR (300 MHz, CDCl ₃ ) δ 12.14-11.95 (m, 1H), 8.33 (d, J=8.0 Hz, 1H), 7.98 (d, J=5, 2 Hz, 1H), 7.21 (d, J=1.5 Hz, 2H), 7.19-6.99 (m, 4H), 6.86 (d, J=5.2 Hz, 1H) , 5.69 (dc, J=9.8, 6.1 Hz, 1H), 4.55 (n, J=7.3 Hz, 1H), 3.94 (d, J=9.9 Hz, 1H), 3.94 (s, 3H), 2.31 (s, 3H), 2.27 (s, 3H), 1.25 (d, J=6.0 Hz, 3H), 1.10 ( d, J=7.2Hz, 3H) 122 ... (Thin Film) 3367, 2986, 1737, 1647, 1611, 1482, 1452, 1215, 1148, 1057 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₅ H ₂₅ F ₂ N ₂ O ₆ , 487.1675; found 487,1686 ¹ H NMR (300 MHz, CDCl ₃ ) δ 12.00 (d, J=0.6 Hz, 1H), 8.41 (d, J=8.1 Hz, 1H), 7.97 (d, J =5.2Hz, 1H), 7.87-7.75(m, 1H), 7.48(tt, J=8.0, 1.5Hz, 1H), 7.28-7.12( m, 3H), 7.10-6.98 (m, 1H), 6.99-6.86 (m, 2H), 6.90-6.82 (m, 1H), 6.26 (cd, J=6.3, 1.5 Hz, 1H), 4.73-4.57 (m, 1H), 3.94 (s, 3H), 3.19 (dd, J=2.8, 1, 9 Hz, 1H), 1.28 (d, J=6.3 Hz, 3H), 1.27 (d, J=7.2 Hz, 3H)
¹⁹ F NMR (471 MHz, CDCl ₃ ) δ -111.85 - -112.11 (m), -112.15 - -112.47 (m) 123 ... (Thin Film) 3285, 2981, 2107, 1736, 1648, 1528, 1263, 1050 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₉ H ₂₇ N ₂ O ₅ , 483.1914; found 483,1919 ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.06 (d, J=0.6 Hz, 1H), 8.33 (d, J=8.0 Hz, 1H), 7.98 (d, J =5.2 Hz, 1H), 7.45-7.40 (m, 2H), 7.40-7.35 (m, 2H), 7.28-7.18 (m, 4H), 6, 86 (d, J=5.2 Hz, 1H), 5.78 (dc, J=9.8, 6.1 Hz, 1H), 4.61-4.45 (m, 1H), 4.07 (d, J=9.8 Hz, 1H), 3.94 (s, 3H), 3.05 (s, 1H), 3.03 (s, 1H), 1.25 (d, J=6, 2 Hz, 3H), 1.04 (d, J=7.2 Hz, 3H) 124 ... (Thin Film) 3368, 2963, 1735, 1648, 1527, 1480, 1450, 1280, 1263, 1142, 1053 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₉ H ₃₅ N ₂ O ₅ , 491.2540; found 491,2551 ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.12 (s, 1H), 8.37 (d, J=8.0 Hz, 1H), 7.98 (d, J=5.2 Hz, 1H ), 7.24-7.18 (m, 4H), 7.14-7.08 (m, 2H), 7.08-7.02 (m, 2H), 6.85 (d, J=5 .2 Hz, 1H), 5.80 (dc, J=10.1, 6.2 Hz, 1H), 4.63-4.40 (m, 1H), 3.99 (d, J=10, 2 Hz, 1H), 3.93 (s, 3H), 2.65-2.50 (m, 4H), 1.25 (d, J=6.1 Hz, 3H), 1.18 (t, J=7.6Hz, 3H), 1.14(t, J=7.6Hz, 3H), 0.94(d, J=7.2Hz, 3H) 125 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₅ H ₂₆ FN ₂ O ₅ , 453.1820; found 453,1831 ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.08 (d, J=0.6 Hz, 1H), 8.33 (d, J=8.0 Hz, 1H), 7.98 (d, J =5.2Hz, 1H), 7.32-7.20(m, 5H), 7.19-7.10(m, 1H), 6.97(t, J=8.7Hz, 2H) , 6.86 (d, J=5.2 Hz, 1H), 5.78 (dc, J=10.0, 6.2 Hz, 1H), 4.58-4.45 (m, 1H), 4.05 (d, J=10.0 Hz, 1H), 3.94 (s, 3H), 1.26 (d, J=6.2 Hz, 3H), 0.98 (d, J=7 .2 Hz, 3H)
¹³ C NMR (126 MHz, CDCl ₃ ) δ 171.63, 168.54, 161.72 (d, J=245.7 Hz), 155.35, 148.71, 141.10, 140.41, 136 .91 (d, J=3.5 Hz), 130.42, 129.58 (d, J=7.8 Hz), 128.59, 127.95, 126.84, 115.64 (d, J =21.3 Hz), 109.40, 73.39, 57.04, 56.07, 47.83, 19.15, 17.59 127 ... ... ESIMS m/z 589.5 ([M+H] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 11.77 (d, J=0.6 Hz, 1H), 8.25 (d, J=8.0 Hz, 1H), 7.96 (d, J =5.2 Hz, 1H), 7.53 (dd, J=20.0, 2.2 Hz, 2H), 7.35 (dd, J=8.5, 1.8 Hz, 2H), 7 .18 (ddd, J=10.9, 8.5, 2.3 Hz, 2H), 6.88 (d, J=5.2 Hz, 1H), 5.80 (k, J=6.3 Hz, 1H), 4.68-4.47 (m, 1H), 3.95 (s, 3H), 1.27 (d, J=7.3 Hz, 3H), 1.20 (d, J =6.4Hz, 3H)
¹³ C NMR (126 MHz, CDCl ₃ ) δ 170.98, 168.86, 155.52, 148.74, 144.18, 141.99, 140.57, 132.92, 132.87, 132.02 , 131.86, 130.48, 130.37, 129.91, 128.15, 127.74, 125.09, 124.82, 109.64, 78.58, 74.60, 56.11, 48 .05, 17.56, 14.13 128 ... ... ESIMS m/z 555.6 ([M+H] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 11.78 (d, J=0.6 Hz, 1H), 8.25 (d, J=8.0 Hz, 1H), 7.96 (d, J =5.3Hz, 1H), 7.33-7.27(m, 2H), 7.22(dd, J=10.4, 2.2Hz, 1H), 7.08(dddd, J= 19.0, 8.5, 2.1, 0.8 Hz, 2H), 6.88 (d, J=5.2 Hz, 1H), 5.82 (c, J=6.3 Hz, 1H ), 4.65-4.51 (m, 1H), 3.95 (s, 3H), 3.00 (s, 1H), 1.26 (d, J=1.2 Hz, 3H), 1 .20 (d, J=6.3 Hz, 3H)
¹³ C NMR (126 MHz, CDCl ₃ ) δ 170.92, 168.87, 158.04 (d, J=249.8 Hz), 157.99 (d, J=249.5 Hz), 155.54 , 148.76, 145.02 (d, J=5.5 Hz), 142.77 (d, J=6.0 Hz), 140.55, 130.65, 130.55, 129.94, 122 .05 (d, J=3.1 Hz), 121.65 (d, J=3.6 Hz), 120.45 (d, J=17.8 Hz), 120.25 (d, J=17 .7 Hz), 114.56 (d, J=22.1 Hz), 114.26 (d, J=23.0 Hz), 109.62, 78.63, 74.64, 56.12, 48 .02, 17.52, 14.30 129 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₇ H ₂₉ Cl ₂ N ₂ O ₅ , 531.1448; found 531,1454 ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.06 (s, 1H), 8.32 (d, J=8.0 Hz, 1H), 7.98 (d, J=5.2 Hz, 1H ), 7.25 (d, J=9.7 Hz, 1H), 7.19 (d, J=8.2 Hz, 1H), 7.09 (dd, J=4.0, 2.3 Hz , 2H), 7.02 (td, J=8.5, 2.3 Hz, 2H), 6.87 (d, J=5.2 Hz, 1H), 5.71 (dc, J=10, 0, 6.1 Hz, 1H), 4.54 (n, J=7.3 Hz, 1H), 3.99-3.92 (m, 4H), 2.33 (s, 3H), 2, 29 (s, 3H), 1.24 (d, J=6.1 Hz, 3H), 1.07 (d, J=7.2 Hz, 3H)
¹³ C NMR (126 MHz, CDCl ₃ ) δ 171.61, 168.57, 155.39, 148.74, 140.44, 139.53, 139.35, 136.56, 136.15, 133.12 , 132.77, 130.63, 130.59, 130.34, 129.45, 129.12, 126.59, 126.41, 109.44, 73.05, 56.45, 56.08, 47 .85, 20.17, 20.08, 19.15, 17.69 130 ... Thin film) 3376, 2986, 2360, 2107, 1736, 1652, 1604, 1558, 1530, 1508, 1452, 1427, 1381, 1329, 1287, 1262, 1247, 1223, 1187, 1159 , 1137, 1116, 1049, 1015 , 911, 826, 792, 779, 729, 680, 668 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₄ H ₂₂ BrF ₂ N ₂ O ₄ , 521.0709; found 521,0713 ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.63 (s, 1H), 8.32 (d, J=7.9 Hz, 1H), 7.88 (d, J=4.9 Hz, 1H ), 7.62 (d, J=4.9 Hz, 1H), 7.29-7.15 (m, 4H), 7.05-6.85 (m, 4H), 5.74 (dc, J=9.9, 6.2 Hz, 1H), 4.61-4.48 (m, 1H), 4.05 (d, J=9.9 Hz, 1H), 1.25 (d, J =6.1Hz, 3H), 1.06 (d, J=7.2Hz, 3H)
¹³ C NMR (101 MHz, CDCl ₃ ) δ 171.39, 167.69, 161.76 (d, J=246.1 Hz), 161.65 (d, J=246.0 Hz), 155.39 , 139.43, 136.82 (d, J=3.4 Hz), 136.63 (d, J=3.1 Hz), 132.21, 131.44, 129.47 (d, J=8 .0 Hz), 129.44 (d, J=7.9 Hz), 122.15, 115.76 (d, J=21.3 Hz), 115.42 (d, J=21.3 Hz) , 73.47, 56.15, 48.05, 19.11, 17.61
¹⁹ F NMR (471 MHz, CDCl ₃ ) δ -115.26 - -115.47 (m), -115.64 (ddd, J=13.7, 8.9, 5.2 Hz) 131 ... (Thin Film) 3373, 2940, 1739, 1651, 1609, 1577, 1518, 1481, 1454, 1436, 1382, 1324, 1283, 1243, 1210, 1149, 1120, 1054, 954, 9 24, 872, 850, 824, 801, 754, 733 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₅ H ₂₃ F ₄ N ₂ O ₅ , 507.1538; found 507,1543 ¹ H NMR (300 MHz, CDCl ₃ ) δ 12.01 (d, J=0.6 Hz, 1H), 8.31 (d, J=8.0 Hz, 1H), 7.98 (d, J =5.2 Hz, 1H), 7.18-6.91 (m, 5H), 6.88 (d, J=5.2 Hz, 1H), 5.66 (dc, J=9.4, 6.2 Hz, 1H), 4.64-4.49 (m, 1H), 4.01 (d, J=9.4 Hz, 1H), 3.95 (s, 3H), 1.32- 1.21 (m, 4H), 1.16 (d, J=7.2 Hz, 3H)
¹⁹ F NMR (471 MHz, CDCl ₃ ) δ -136.05 - -136.27 (m), -136.61 (ddd, J=20.1, 11.4, 8.1 Hz), -139, 14 - -139.32 (m), -139.45 - -139.68 (m) 132 ... (Thin Film) 3372, 2983, 1737, 1649, 1601, 1576, 1529, 1498, 1481, 1453, 1439, 1381, 1323, 1245, 1184, 1145, 1096, 1060, 953, 9 09, 864, 849, 824, 800, 730, 689 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₅ H ₂₃ Cl ₂ F ₂ N ₂ O ₅ , 539.0947; found 539.0954 ¹ H NMR (300 MHz, CDCl ₃ ) δ 12.02 (d, J=0.6 Hz, 1H), 8.31 (d, J=7.9 Hz, 1H), 7.97 (d, J =5.2Hz, 1H), 7.27(td, J=7.3, 2.1Hz, 2H), 7.19-6.98(m, 4H), 6.88(d, J= 5.2 Hz, 1H), 5.66 (dc, J=9.5, 6.1 Hz, 1H), 4.66-4.48 (m, 1H), 4.01 (d, J=9 .6 Hz, 1H), 3.95 (s, 3H), 1.26 (d, J=6.2 Hz, 3H), 1.17 (d, J=7.2 Hz, 3H)
¹⁹ F NMR (471 MHz, CDCl ₃ ) δ -116.83 - -116.94 (m), -117.22 - -117.34 (m) 133 ... (Thin Film) 3372, 2935, 2257, 1735, 1649, 1576, 1528, 1501, 1481, 1452, 1439, 1380, 1324, 1281, 1262, 1241, 1206, 1149, 1118, 1051, 952, 908, 849, 821, 800, 729 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₇ H ₂₉ F ₂ N ₂ O ₅ , 499.2039; found 499,2046 ¹ H NMR (300 MHz, CDCl ₃ ) δ 12.08 (d, J=0.5 Hz, 1H), 8.34 (d, J=8.0 Hz, 1H), 7.97 (d, J =5.2 Hz, 1H), 7.12-6.98 (m, 5H), 6.97-6.79 (m, 3H), 5.70 (dc, J=10.1, 6.1 Hz, 1H), 4.65-4.46 (m, 1H), 3.94 (s, 3H), 2.21 (dd, J=9.8, 1.9 Hz, 6H), 1.24 (d, J=6.1Hz, 3H), 1.06 (d, J=7.2Hz, 3H)
¹⁹ F NMR (471 MHz, CDCl ₃ ) δ -119.78 - -120.04 (m), -120.30 - -120.53 (m) 135 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₅ H ₂₅ F ₂ N ₂ O ₅ , 471.1726; found 471,1742 ¹ H NMR (300 MHz, CDCl ₃ ) δ 12.08 (d, J=0.6 Hz, 1H), 8.20 (d, J=8.0 Hz, 1H), 8.00 (d, J =5.2 Hz, 1H), 7.26-7.13 (m, 4H), 7.02-6.83 (m, 5H), 5.69 (dc, J=9.0, 6.2 Hz, 1H), 4.53 (dc, J=8.0, 7.2 Hz, 1H), 4.05 (d, J=9.1 Hz, 1H), 3.96 (s, 3H), 1.34 (d, J=1.2 Hz, 3H), 1.22 (d, J=6.2 Hz, 3H)
¹³ C NMR (126 MHz, CDCl ₃ ) δ 171.27, 168.54, 162.68, 162.58, 160.73, 160.63, 155.43, 148.77, 140.44, 136.81 136.78 136.46 136.43 130.33 129.72 129.66 129.63 129.57 115.74 115.57 115.43 115.26 109 .49, 73.33, 56.11, 55.65, 47.80, 18.95, 17.74 136 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₅ H ₂₃ C ₁₄ N ₂ O ₅ , 571.0356; found 571.0367 ¹ H NMR (300 MHz, CDCl ₃ ) δ 12.00 (s, 1H), 8.30 (d, J=7.8 Hz, 1H), 7.98 (d, J=5.1 Hz, 1H ), 7.42-7.28 (m, 4H), 7.09 (ddd, J=10.1, 8.3, 2.2 Hz, 2H), 6.87 (d, J=5.2 Hz, 1H), 5.65 (dt, J=12.2, 6.1 Hz, 1H), 4.57 (p, J=7.3 Hz, 1H), 4.00 (d, J=9 .6 Hz, 1H), 3.95 (s, 3H), 1.27 (d, J=5.9 Hz, 3H), 1.17 (d, J=7.2 Hz, 3H)
¹³ C NMR (126 MHz, CDCl ₃ ) δ 171.45, 168.64, 155.42, 148.74, 140.51, 140.21, 140.16, 133.11, 132.76, 131.70 , 131.38, 130.97, 130.67, 130.27, 130.20, 130.08, 127.25, 127.17, 109.53, 72.38, 56.09, 55.71, 47 .87, 19.03, 17.71 137 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₅ H ₂₃ Cl ₂ F ₂ N ₂ O ₅ , 539.0947; found 539.0953 ¹ H NMR (300 MHz, CDCl ₃ ) δ 11.99 (s, 1H), 8.30 (d, J=8.0 Hz, 1H), 7.98 (d, J=5.2 Hz, 1H ), 7.42-7.19 (m, 2H), 7.08-6.94 (m, 4H), 6.90-6.84 (m, 1H), 5.67 (dc, J=9 .4, 6.2 Hz, 1H), 4.65-4.48 (m, 1H), 4.03 (d, J=9.4 Hz, 1H), 3.95 (s, 3H), 1 .27 (d, J=6.1 Hz, 3H), 1.16 (d, J=7.2 Hz, 3H)
¹³ C NMR (126 MHz, CDCl ₃ ) δ 171.41, 168.64, 158.16 (d, J=250.2 Hz), 158.01 (d, J=250.1 Hz), 155.42 , 148.75, 140.91 (d, J=6.1 Hz), 140.83 (d, J=6.3 Hz), 140.51, 131.12, 130.81, 130.20, 124 .67-123.96 (m), 120.11 (d, J=17.5 Hz), 119.82 (d, J=17.7 Hz), 116.78-116.06 (m), 109 .52, 72.44, 56.09, 47.85, 18.99, 17.71 138 ... ... HRMS-ESI (m/z) [M] ⁺ calculated for C ₂₈ H ₃₀ N ₂ O ₈ , 522.2002; found 522,2006 ¹ H NMR (500 MHz, CDCl ₃ ) δ 8.27 (d, J=5.4 Hz, 1H), 8.13 (d, J=8.0 Hz, 1H), 7.50-7.44 (m, 4H), 7.27 (ddd, J=11.5, 8.5, 7.0 Hz, 4H), 7.20-7.14 (m, 2H), 6.94 (d, J =5.4Hz, 1H), 6.01(k, J=6.3Hz, 1H), 5.75-5.62(m, 2H), 4.63-4.52(m, 1H) , 3.90 (s, 3H), 2.94 (s, 1H), 2.06 (s, 3H), 1.22 (d, J=6.3 Hz, 3H), 1.03 (d, J=7.2Hz, 3H)
¹³ C NMR (126 MHz, CDCl ₃ ) δ 171.88, 170.27, 163.03, 160.26, 145.73, 144.99, 143.90, 142.88, 142.57, 128.31 , 128.28, 127.14, 127.07, 125.56, 125.54, 109.58, 89.49, 79.55, 75.21, 56.19, 48.10, 30.93, 20 .87, 17.75, 14.36 139 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₇ H ₂₉ N ₂ O ₆ , 477.2025; found 477,2019 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.41 (d, J=7.8 Hz, 1H), 8.30 (d, J=5.4 Hz, 1H), 7.38-7.10 (m, 10H), 6.97 (d, J=5.4 Hz, 1H), 5.82 (dc, J=10.0, 6.2 Hz, 1H), 4.52 (dt, J= 8.2, 7.1 Hz, 1H), 4.05 (d, J=10.1 Hz, 1H), 3.87 (s, 3H), 2.37 (s, 3H), 1.24 ( d, J=6.1 Hz, 3H), 0.89 (d, J=7.1 Hz, 3H)
¹³ C NMR (101 MHz, CDCl ₃ ) δ 172.23, 168.89, 162.28, 159.42, 146.66, 141.55, 141.44, 141.25, 137.45, 128.77 , 128.50, 128.13, 128.11, 126.89, 126.67, 109.73, 73.32, 57.90, 56.27, 47.85, 20.75, 19.25, 17 .92 140 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₉ H ₃₃ N ₂ O ₆ , 505.2338; found 505,2324 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.35 (d, J=7.7 Hz, 1H), 8.30 (d, J=5.4 Hz, 1H), 7.34-7.09 (m, 10H), 6.95 (d, J=5.5 Hz, 1H), 5.81 (dc, J=10.0, 6.2 Hz, 1H), 4.62-4.44 ( m, 1H), 4.05 (d, J=10.0 Hz, 1H), 3.85 (s, 3H), 2.93 (hept., J=7.0 Hz, 1H), 1.34 (d, J=7.0Hz, 6H), 1.24 (d, J=6.2Hz, 3H), 0.88 (d, J=1.2Hz, 3H)
¹³ C NMR (101 MHz, CDCl ₃ ) δ 174.69, 172.33, 162.28, 159.39, 146.56, 141.95, 141.45, 141.27, 137.61, 128.76 , 128.50, 128.14, 128.12, 126.89, 126.67, 109.58, 73.28, 57.90, 56.27, 47.83, 33.94, 19.24, 18 .82, 17.96 141 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₈ H ₃₁ N ₂ O ₇ , 507.2131; found 507.2125 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.25 (d, J=5.4 Hz, 1H), 8.22 (d, J=1.9 Hz, 1H), 7.34-7.09 (m, 10H), 6.92 (d, J=5.4 Hz, 1H), 5.83 (dc, J=10.1, 6.2 Hz, 1H), 5.72 (d, J= 0.7 Hz, 2H), 4.60-4.49 (m, 1H), 4.06 (d, J=10.1 Hz, 1H), 3.88 (s, 3H), 2.05 ( s, 3H), 1.25 (d, J=6.1 Hz, 3H), 0.91 (d, J=1.2 Hz, 3H)
¹³ C NMR (101 MHz, CDCl ₃ ) δ 172.33, 170.25, 162.88, 160.24, 145.70, 143.91, 142.54, 141.48, 141.25, 128.76 , 128.49, 128.12, 128.09, 126.89, 126.65, 109.56, 89.50, 73.27, 57.92, 56.17, 48.07, 20.86, 19 .25, 17.73 142 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₀ H ₃₅ N ₂ O ₇ , 535.2444; found 535,2431 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.28 (d, J=7.9 Hz, 1H), 8.25 (d, J=5.3 Hz, 1H), 7.36-7.08 (m, 10H), 6.92 (d, J=5.4 Hz, 1H), 5.83 (dc, J=10.1, 6.2 Hz, 1H), 5.79-5.69 ( m, 2H), 4.62-4.44 (m, 1H), 4.06 (d, J=10.1 Hz, 1H), 3.86 (s, 3H), 2.53 (hept., .7=7.0 Hz, 1H), 1.25 (d, J=6.2 Hz, 3H), 1.13 (d, J=7.0 Hz, 6H), 0.91 (d, J =7.2Hz, 3H)
¹³ C NMR (101 MHz, CDCl ₃ ) δ 176.22, 172.34, 162.85, 160.23, 145.55, 144.16, 142.18, 141.48, 141.26, 128.76 , 128.49, 128.12, 128.09, 126.89, 126.65, 109.48, 89.90, 73.26, 57.93, 56.12, 48.07, 33.85, 19 .26, 18.68, 17.74 143 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₃ H ₂₅ N ₂ O ₆ S ₂ , 489.1154; found 489,1154 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.49 (d, J=8.1 Hz, 1H), 8.31 (d, J=5.5 Hz, 1H), 7.21-7.13 (m, 2H), 7.03-6.97 (m, 2H), 6.95-6.86 (m, 3H), 5.54 (dc, J=7.3, 6.2 Hz, 1H ), 4.70-4.61 (m, 2H), 3.88 (s, 3H), 2.39 (s, 3H), 1.28 (d, J=6.2 Hz, 3H), 1 .17 (d, J=7.2 Hz, 3H)
¹³ C NMR (101 MHz, CDCl ₃ ) δ 172.03, 168.89, 162.33, 159.44, 146.66, 143.85, 142.75, 141.50, 137.48, 126.75 , 126.56, 126.06, 125.43, 124.60, 124.55, 109.78, 74.58, 56.28, 47.96, 47.41, 20.76, 18.68, 18 ,14 144 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₄ H ₂₇ N ₂ O ₇ S ₂ , 519.1259; found 519,1258 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.30 (d, J=7.9 Hz, 1H), 8.26 (d, J=5.4 Hz, 1H), 7.21-7.13 (m, 2H), 7.02 (ddd, J=3.5, 1.2, 0.6 Hz, 1H), 6.96-6.88 (m, 4H), 5.73 (d, J =0.7 Hz, 2H), 5.55 (dc, J=7.4, 6.2 Hz, 1H), 4.75-4.60 (m, 2H), 3.89 (s, 3H) , 2.06 (s, 3H), 1.29 (d, J=6.3 Hz, 3H), 1.19 (d, J=7.2 Hz, 3H)
¹³ C NMR (101 MHz, CDCl ₃ ) δ 172.13, 170.25, 162.91, 160.26, 145.69, 143.96, 143.86, 142.81, 142.46, 126.74 , 126.55, 126.03, 125.42, 124.58, 124.54, 109.59, 89.52, 74.55, 56.19, 48.18, 47.42, 20.87, 18 .70, 17.95 145 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₇ H ₂₇ F ₂ N ₂ O ₆ , 513.1837; found 513,1835 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.48-8.37 (m, 1H), 8.30 (d, J=5.4 Hz, 1H), 7.29-7.18 (m, 4H), 7.05-6.90 (m, 5H), 5.72 (dc, J=9.7, 6.2 Hz, 1H), 4.55 (dc, J=8.3, 7, 2 Hz, 1H), 4.05 (d, J=9.6 Hz, 1H), 3.88 (s, 3H), 2.38 (s, 3H), 1.22 (d, J=6, 1Hz, 3H), 1.00 (d, J=7.2Hz, 3H)
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -115.58, -115.93 146 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₈ H ₂₉ F ₂ N ₂ O ₇ , 543.1943; found 543,1938 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.26 (d, J=5.4 Hz, 1H), 8.22 (d, J=7.8 Hz, 1H), 7.32-7.16 (m, 4H), 7.05-6.89 (m, 5H), 5.78-5.68 (m, 1H), 5.72 (s, 2H), 4.64-4.50 (m , 1H), 4.06 (d, J=9.7 Hz, 1H), 3.90 (s, 3H), 2.06 (s, 3H), 1.24 (d, J=6.1 Hz , 3H), 1.00 (d, J=7.2 Hz, 3H)
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -115.59, -115.97 147 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₀ H ₃₅ N ₂ O ₈ , 551.2393; found 551.2396 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.34 (d, J=7.9 Hz, 1H), 8.25 (d, J=5.4 Hz, 1H), 7.39-7.16 (m, 10H), 6.94 (d, J=5.4 Hz, 1H), 5.97 (q, J=6.2 Hz, 1H), 5.78-5.61 (m, 2H) , 4.74-4.56 (m, 1H), 3.90 (s, 3H), 3.42 (dc, J=9.2, 7.0 Hz, 1H), 3.21 (dc, J =9.2, 7.0 Hz, 1H), 2.05 (s, 3H), 1.25 (d, J=7.2 Hz, 3H), 1.19 (t, J=6.9 Hz , 3H), 1.12 (d, J=6.3 Hz, 3H)
¹³ C NMR (101 MHz, CDCl ₃ ) δ 172.13, 170.23, 162.87, 160.27, 145.64, 144.02, 142.35, 142.09, 140.72, 128.24 , 127.84, 127.81, 127.70, 127.27, 127.18, 109.57, 89.52, 84.04, 74.08, 59.96, 56.18, 48.26, 20 .86, 18.23, 15.70, 14.95 148 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₈ H ₂₇ F ₄ N ₂ O ₇ , 579.1754; found 579,1756 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.26 (d, J=5.3 Hz, 1H), 8.22 (d, J=7.8 Hz, 1H), 7.38 (td, J =8.6, 6.2 Hz, 1H), 7.24 (td, J=8.4, 6.3 Hz, 1H), 6.96 (d, J=5.5 Hz, 1H), 6 .88-6.69 (m, 4H), 5.88-5.75 (m, 1H), 5.73 (s, 2H), 4.69 (d, J=9.8 Hz, 1H), 4.65-4.55 (m, 1H), 3.91 (s, 3H), 2.07 (s, 3H), 1.29 (d, J=6.2 Hz, 3H), 1.10 (d, J=7.2Hz, 3H)
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -111.11 (d, J=7.6 Hz), -111.57 (d, J=7.5 Hz), -111.99 (dd, J= 7.7, 2.6Hz), -112.76 (dd, J=7.6, 2.5Hz) 149 ... ... HRMS-ESI (m/z) [M-OCH ₃ ]+ calculated for C ₂₈ H ₂₉ N ₂ O ₇ , 505.1975; found 505,1975 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.33 (d, J=7.9 Hz, 1H), 8.25 (d, J=5.4 Hz, 1H), 7.40-7.18 (m, 10H), 6.94 (d, J=5.4 Hz, 1H), 5.97 (q, J=6.2 Hz, 1H), 5.81-5.63 (m, 2H) , 4.72-4.52 (m, 1H), 3.90 (s, 3H), 3.17 (s, 3H), 2.05 (s, 3H), 1.24 (d, J=7 .2 Hz, 3H), 1.12 (d, J=6.3 Hz, 3H)
¹³ C NMR (101 MHz, CDCl ₃ ) δ 172.09, 170.24, 162.88, 160.27, 145.65, 144.02, 142.35, 141.39, 140.04, 128.50 , 128.08, 127.87, 127.71, 127.45, 127.28, 109.57, 89.53, 84.46, 73.81, 56.19, 52.59, 48.25, 20 .86, 18.18, 14.98 150 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₇ H ₂₅ F ₄ N ₂ O ₆ , 549.1648; found 549,1645 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.39 (d, J=8.1 Hz, 1H), 8.31 (d, J=5.4 Hz, 1H), 7.37 (td, J =8.5, 6.1 Hz, 1H), 7.23 (td, J=8.5, 6.2 Hz, 1H), 7.00 (d, J=5.5 Hz, 1H), 6 .90-6.68 (m, 4H), 5.89-5.71 (m, 1H), 4.69 (d, J=9.8 Hz, 1H), 4.62-4.51 (m , 1H), 3.90 (s, 3H), 2.39 (s, 3H), 1.28 (d, J=6.2 Hz, 3H), 1.09 (d, J=7.2 Hz , 3H)
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -111.11 (d, J=7.7 Hz), -111.55 (d, J=7.5 Hz), -112.01 (dd, J= 7.7, 2.6Hz), -112.80 (dd, J=7.6, 2.6Hz) 152 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₇ H ₂₈ FN ₂ O ₆ , 495.1931; found 495,1926 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.38 (d, J=8.2 Hz, 1H), 8.30 (d, J=5.4 Hz, 1H), 7.50-7.37 (m, 4H), 7.37-7.19 (m, 6H), 6.98 (d, J=5.5 Hz, 1H), 5.98 (dc, J=25.1, 6.4 Hz, 1H), 4.63-4.54 (m, 1H), 3.87 (s, 3H), 2.37 (s, 3H), 1.30 (d, J=6.5 Hz, 3H ), 0.88 (d, J=7.2 Hz, 3H)
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -168.48 153 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₈ H ₃₀ FN ₂ O ₇ , 525.2037; found 525,2033 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.26 (d, J=5.3 Hz, 1H), 8.20 (d, J=7.7 Hz, 1H), 7.49-7.40 (m, 4H), 7.36-7.21 (m, 6H), 6.93 (d, J=5.5 Hz, 1H), 5.99 (dc, J=25.2, 6.4 Hz, 1H), 5.71 (s, 2H), 4.68-4.49 (m, 1H), 3.89 (s, 3H), 2.05 (s, 3H), 1.31 (d , J=6.5Hz, 3H), 0.90 (d, J=7.2Hz, 3H)
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -168.67 155 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₉ H ₃₃ N ₂ O ₈ , 537.2237; found 537,2226 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.42 (d, J=8.1 Hz, 1H), 8.30 (d, J=5.4 Hz, 1H), 7.26-7.13 (m, 4H), 6.97 (d, J=5.5 Hz, 1H), 6.85-6.71 (m, 4H), 5.71 (dc, J=9.9, 6.2 Hz, 1H), 4.64-4.47 (m, 1H), 3.96 (d, J=9.8 Hz, 1H), 3.87 (s, 3H), 3.74 (s, 3H ), 3.72 (s, 3H), 2.38 (s, 3H), 1.22 (d, J=6.1 Hz, 3H), 0.98 (d, J=7.2 Hz, 3H )
¹³ C NMR (101 MHz, CDCl ₃ ) δ 172.21, 168.88, 162.28, 159.42, 158.33, 158.20, 146.66, 141.53, 137.43, 133.90 , 133.82, 129.02, 129.00, 114.09, 113.83, 109.74, 73.54, 56.26, 56.08, 55.19, 47.90, 20.74, 19 .22, 18.08 156 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₇ H ₂₇ F ₂ N ₂ O ₆ , 513.1837; found 513,1833 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.41 (d, J=7.6 Hz, 1H), 8.31 (d, J=5.5 Hz, 1H), 7.32-7.18 (m, 2H), 7.12-6.82 (m, 7H), 5.73 (dc, J=9.7, 6.2 Hz, 1H), 4.64-4.43 (m, 1H ), 4.06 (d, J=9.8 Hz, 1H), 3.89 (s, 3H), 2.38 (s, 3H), 1.25 (d, J=6.2 Hz, 3H ), 0.99 (d, J=7.2 Hz, 3H)
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -112.15, -112.56 157 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₇ H ₂₇ Cl ₂ N ₂ O ₆ , 545.1246; found 545,1239 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.41 (d, J=7.7 Hz, 1H), 8.31 (d, J=5.4 Hz, 1H), 7.31-7.10 (m, 8H), 6.99 (d, J=5.5 Hz, 1H), 5.72 (dc, J=9.8, 6.0 Hz, 1H), 4.59-4.50 ( m, 1H), 4.01 (d, J=9.8 Hz, 1H), 3.88 (s, 3H), 2.38 (s, 3H), 1.24 (d, J=6.1 Hz, 3H), 1.00 (d, J=7.1 Hz, 3H)
¹³ C NMR (101 MHz, CDCl ₃ ) δ 172.10, 168.87, 162.33, 159.43, 146.68, 142.60, 142.44, 141.40, 137.46, 134.67 , 134.38, 130.21, 129.95, 128.46, 128.34, 128.10, 127.45, 127.17, 126.23, 126.13, 109.80, 72.61, 56 .98, 56.28, 47.82, 20.75, 19.12, 17.98 158 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₀ H ₃₅ N ₂ O ₉ , 567.2342; found 567.2338 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.26 (d, J=5.4 Hz, 1H), 8.23 (d, J=8.0 Hz, 1H), 7.24-7.14 (m, 4H), 6.93 (d, J=5.4 Hz, 1H), 6.85-6.75 (m, 4H), 5.77-5.68 (m, 1H), 5, 72 (s, 2H), 4.63-4.50 (m, 1H), 3.97 (d, J=9.9 Hz, 1H), 3.89 (s, 3H), 3.75 (s , 3H), 3.73 (s, 3H), 2.05 (s, 3H), 1.23 (d, J=6.2 Hz, 3H), 0.99 (d, J=7.2 Hz , 3H)
¹³ C NMR (101 MHz, CDCl ₃ ) δ 172.34, 170.24, 162.88, 160.24, 158.33, 158.20, 145.70, 143.91, 142.54, 133.95 , 133.82, 129.00, 114.09, 113.83, 109.55, 89.51, 73.49, 56.17, 56.10, 55.20, 48.12, 20.85, 19 .23, 17.90 159 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₈ H ₂₉ F ₂ N ₂ O ₇ , 543.1943; found 543,1941 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.26 (d, J=5.4 Hz, 1H), 8.23 (d, J=7.9 Hz, 1H), 7.32-7.18 (m, 2H), 7.14-7.03 (m, 2H), 7.04-6.80 (m, 5H), 5.82-5.67 (m, 1H), 5.72 (s , 2H), 4.65-4.48 (m, 1H), 4.07 (d, J=9.9 Hz, 1H), 3.90 (s, 3H), 2.06 (s, 3H) , 1.26 (d, J=6.1 Hz, 3H), 1.00 (d, J=7.2 Hz, 3H)
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -112.16, -112.59 160 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₈ H ₂₉ Cl ₂ N ₂ O ₇ , 575.1352; found 575,1349 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.26 (d, J=5.3 Hz, 1H), 8.22 (d, J=7.6 Hz, 1H), 7.33-7.10 (m, 8H), 6.94 (d, J=5.4 Hz, 1H), 5.80-5.65 (m, 1H), 5.72 (s, 2H), 4.60-4, 52 (m, 1H), 4.03 (d, J=9.8 Hz, 1H), 3.90 (s, 3H), 2.06 (d, J=1.8 Hz, 3H), 1, 26 (d, J=6.0 Hz, 3H), 1.02 (d, J=7.1 Hz, 3H)
¹³ C NMR (101 MHz, CDCl ₃ ) δ 172.34, 170.24, 162.88, 160.24, 158.33, 158.20, 145.70, 143.91, 142.54, 133.95 , 133.82, 129.00, 114.09, 113.83, 109.55, 89.51, 73.49, 56.17, 56.10, 55.20, 48.12, 20.85, 19 .23, 17.90 161 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₇ H ₂₇ N ₂ O ₆ , 475.1869; found 475,1865 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.77-8.53 (m, 1H), 8.40-8.29 (m, 1H), 7.79-7.62 (m, 3H), 7.61-7.47 (m, 1H), 7.47-7.34 (m, 2H), 7.34-7.20 (m, 2H), 7.05-6.94 (m, 1H ), 5.83-5.66 (m, 1H), 4.93-4.77 (m, 1H), 4.37-4.21 (m, 1H), 3.89 (s, 3H), 2.47-2.37 (m, 3H), 1.63-1.47 (m, 3H), 0.84-0.67 (m, 3H) 162 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₇ H ₂₇ N ₂ O ₇ , 491.1818; found 491,1813 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.58-8.43 (m, 1H), 8.40-8.32 (m, 1H), 7.36-7.19 (m, 4H), 7.13-7.03(m, 4H), 7.02-6.97(m, 1H), 5.17-5.05(m, 1H), 4.77-4.64(m, 1H ), 4.35-4.19 (m, 1H), 3.96-3.85 (m, 3H), 2.40 (d, J=3.6 Hz, 3H), 1.50-1, 41 (m, 3H), 1.07-0.93 (m, 3H) 163 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₈ H ₂₉ N ₂ O ₇ , 505.1975; found 505,1961 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.52-8.37 (m, 1H), 8.32-8.24 (m, 1H), 7.80-7.63 (m, 3H), 7.61-7.47(m, 1H), 7.45-7.22(m, 4H), 7.01-6.92(m, 1H), 5.83-5.68(m, 3H ), 4.97-4.73 (m, 1H), 4.38-4.19 (m, 1H), 3.92 (s, 3H), 2.07 (s, 3H), 1.64- 1.49 (m, 3H), 0.90-0.66 (m, 3H) 164 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₈ H ₂₉ N ₂ O ₈ , 521.1924; found 521,1913 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.39-8.25 (m, 2H), 7.39-7.20 (m, 4H), 7.15-7.00 (m, 4H), 6.99-6.92 (m, 1H), 5.81-5.72 (m, 2H), 5.16-5.09 (m, 1H), 4.79-4.67 (m, 1H ), 4.37-4.17 (m, 1H), 3.91 (s, 3H), 2.08 (s, 3H), 1.51-1.43 (m, 3H), 1.09- 0.93 (m, 3H) 165 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₇ H ₂₇ Br ₂ N ₂ O ₆ , 633.0236; found 633.0230 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.39 (d, J=6.8 Hz, 1H), 8.31 (d, J=5.4 Hz, 1H), 7.45-7.31 (m, 4H), 7.18-7.06 (m, 4H), 7.00 (d, J=5.5 Hz, 1H), 5.71 (dc, J=9.5, 6.2 Hz, 1H), 4.65-4.46 (m, 1H), 4.00 (d, J=9.5 Hz, 1H), 3.89 (s, 3H), 2.38 (s, 3H ), 1.22 (d, J=6.2 Hz, 3H), 1.02 (d, J=7.2 Hz, 3H)
¹³ C NMR (101 MHz, CDCl ₃ ) δ 172.05, 168.89, 162.33, 159.47, 146.65, 141.39, 139.74, 139.71, 137.49, 131.97 , 131.68, 129.89, 129.78, 121.06, 120.79, 109.84, 72.56, 56.41, 56.30, 47.83, 20.76, 19.09, 17 .98 166 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₅ H ₂₉ N ₂ O ₆ S ₂ , 517.1467; found 517,1465 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.51 (d, J=8.1 Hz, 1H), 8.32 (d, J=5.4 Hz, 1H), 6.99 (d, J =5.5 Hz, 1H), 6.74 (d, J=3.4 Hz, 1H), 6.67 (d, J=2.6 Hz, 1H), 6.60-6.42 (m , 2H), 5.53-5.39 (m, 1H), 4.72-4.58 (m, 1H), 4.44 (d, J=7.1 Hz, 1H), 3.88 ( s, 3H), 2.41-2.38 (m, 9H), 1.27 (d, J=6.2 Hz, 3H), 1.22 (d, J=7.2 Hz, 3H)
¹³ C NMR (101 MHz, CDCl ₃ ) δ 172.07, 168.90, 162.33, 159.44, 146.66, 141.64, 141.56, 140.54, 138.98, 138.92 , 137.47, 125.77, 125.08, 124.66, 124.42, 109.76, 74.45, 56.28, 48.01, 47.83, 20.75, 18.64, 18 .21, 15.25 167 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₉ H ₃₃ N ₂ O ₆ , 505.2338; found 505,2345 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.42 (d, J=8.0 Hz, 1H), 8.29 (d, J=5.4 Hz, 1H), 7.20-7.10 (m, 4H), 7.10-6.99 (m, 4H), 6.96 (d, J=5.5 Hz, 1H), 5.77 (dc, J=10.0, 6.2 Hz, 1H), 4.65-4.45 (m, 1H), 3.98 (d, J=10.0 Hz, 1H), 3.85 (s, 3H), 2.37 (s, 3H ), 2.26 (s, 3H), 2.23 (s, 3H), 1.23 (d, J=6.1 Hz, 3H), 0.93 (d, J=7.1 Hz, 3H )
¹³ C NMR (101 MHz, CDCl ₃ ) δ 172.23, 168.90, 162.28, 159.42, 146.67, 141.58, 138.67, 138.57, 137.44, 136.33 , 136.02, 129.41, 129.11, 127.94, 127.91, 109.74, 73.44, 57.06, 56.27, 47.91, 20.97, 20.94, 20 .76, 19.26, 17.99 168 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₁ H ₃₇ N ₂ O ₆ , 533.2651; found 533.2655 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.36 (d, J=8.8 Hz, 1H), 8.29 (d, J=5.4 Hz, 1H), 7.19-7.12 (m, 4H), 7.10-6.98 (m, 4H), 6.94 (d, J=5.5 Hz, 1H), 5.76 (dc, J=10.0, 6.2 Hz, 1H), 4.60-4.45 (m, 1H), 3.97 (d, J=9.9 Hz, 1H), 3.84 (s, 3H), 3.00-2.85 (m, 1H), 2.26 (s, 3H), 2.24 (s, 3H), 1.34 (d, J=7.0 Hz, 6H), 1.22 (d, J=6, 1 Hz, 3H), 0.93 (d, J=7.2 Hz, 3H)
¹³ C NMR (101 MHz, CDCl ₃ ) δ 174.69, 172.32, 162.28, 159.39, 146.57, 141.98, 138.67, 138.59, 137.60, 136.31 , 136.01, 129.40, 129.10, 127.95, 127.93, 109.58, 73.40, 57.05, 56.27, 47.89, 33.95, 20.97, 20 .94, 19.25, 18.84, 18.04 169 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₈ H ₂₉ Br ₂ N ₂ O ₇ , 663.0341; found 663.0336 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.26 (d, J=5.4 Hz, 1H), 8.21 (d, J=7.8 Hz, 1H), 7.45-7.33 (m, 4H), 7.22-7.03 (m, 4H), 6.95 (d, J=5.4 Hz, 1H), 5.83-5.61 (m, 1H), 5, 72 (s, 2H), 4.56 (n, J=7.3 Hz, 1H), 4.01 (d, J=9.6 Hz, 1H), 3.90 (s, 3H), 2, 06 (s, 3H), 1.24 (d, J=6.2Hz, 3H), 1.02 (d, J=7.2Hz, 3H)
¹³ C NMR (101 MHz, CDCl ₃ ) δ 172.18, 170.25, 162.91, 160.27, 145.69, 143.97, 142.36, 139.81, 139.71, 131.97 , 131.68, 129.87, 129.76, 121.06, 120.77, 109.63, 89.49, 72.51, 56.46, 56.20, 48.06, 20.87, 19 .12, 17.81 170 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₆ H ₃₁ N ₂ O ₇ S ₂ , 547.1572; found 547,1585 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.31 (d, J=7.9 Hz, 1H), 8.27 (d, J=5.3 Hz, 1H), 6.94 (d, J =5.4Hz, 1H), 6.75(d, J=3.4Hz, 1H), 6.70-6.62(m, 1H), 6.57-6.50(m, 2H) , 5.77-5.70 (m, 2H), 5.52-5.40 (m, 1H), 4.75-4.58 (m, 1H), 4.45 (d, J=7, 1 Hz, 1H), 3.90 (s, 3H), 2.40 (d, J=1.2 Hz, 3H), 2.39 (d, J=1.1 Hz, 3H), 2.06 (s, 3H), 1.36-1.14 (m, 6H)
¹³ C NMR (101 MHz, CDCl ₃ ) δ 172.17, 170.25, 162.90, 160.26, 145.69, 143.95, 142.56, 141.64, 140.61, 138.96 , 138.93, 125.73, 125.07, 124.65, 124.41, 109.55, 89.54, 74.42, 56.18, 48.23, 47.85, 20.87, 18 .66, 18.03, 15.24 171 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₀ H ₃₅ N ₂ O ₇ , 535.2444; found 535,2449 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.33-8.15 (m, 2H), 7.22-7.10 (m, 4H), 7.10-6.99 (m, 4H), 6.92 (d, J=5.4 Hz, 1H), 5.84-5.69 (m, 3H), 4.55 (p, J=7.3 Hz, 1H), 3.99 (d , J=10.0 Hz, 1H), 3.87 (s, 3H), 2.27 (s, 3H), 2.24 (s, 3H), 2.05 (s, 3H), 1.24 (d, J=6.2Hz, 3H), 0.95 (d, J=7.2Hz, 3H)
¹³ C NMR (101 MHz, CDCl ₃ ) δ 172.34, 170.24, 162.87, 160.24, 145.70, 143.90, 142.59, 138.70, 138.58, 136.32 , 135.99, 129.40, 129.10, 127.93, 127.90, 109.55, 89.51, 73.38, 57.07, 56.17, 48.12, 20.96, 20 .93, 20.86, 19.26, 17.81 173 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₈ H ₂₈ F ₃ N ₂ O ₆ , 545.1899; found 545,1902 ¹ H NMR (300 MHz, CDCl ₃ ) δ 8.42 (d, J=7.7 Hz, 1H), 8.31 (d, J=5.4 Hz, 1H), 7.60-7.50 (m, 2H), 7.47-7.37 (m, 2H), 7.34-7.13 (m, 5H), 6.99 (d, J=5.4 Hz, 1H), 5, 83 (dc, J=9.6, 6.2 Hz, 1H), 4.65-4.45 (m, 1H), 4.14 (d, J=9.7 Hz, 1H), 3.88 (s, 3H), 2.38 (s, 3H), 1.25 (d, J=6.2 Hz, 3H), 0.92 (d, J=7.2 Hz, 3H)
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -62.56 174 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₇ H ₂₇ Cl ₂ N ₂ O ₆ , 545.1246; found 545,1244 ¹ H NMR (300 MHz, CDCl ₃ ) δ 8.40 (d, J=8.1 Hz, 1H), 8.30 (d, J=5.5 Hz, 1H), 7.31-7.12 (m, 8H), 6.99 (d, J=5.5 Hz, 1H), 5.72 (dc, J=9.5, 6.1 Hz, 1H), 4.66-4.47 ( m, 1H), 4.03 (d, J=9.5 Hz, 1H), 3.88 (s, 3H), 2.38 (s, 3H), 1.22 (d, J=6.1 Hz, 3H), 1.01 (d, J=7.1 Hz, 3H)
¹³ C NMR (75 MHz, CDCl ₃ ) δ 172.06, 168.91, 162.33, 159.45, 146.66, 141.36, 139.32, 139.27, 137.47, 132.94 , 132.69, 129.51, 129.41, 129.01, 128.72, 109.85, 72.70, 56.30, 56.27, 47.83, 20.75, 19.09, 17 .98 175 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₉ H ₃₀ F ₃ N ₂ O ₇ , 575.2005; found 575,2011 ¹ H NMR (300 MHz, CDCl ₃ ) δ 8.26 (d, J=5.4 Hz, 1H), 8.22 (d, J=7.8 Hz, 1H), 7.58-7.49 (m, 2H), 7.42 (d, J=8.2 Hz, 2H), 7.35-7.12 (m, 5H), 6.95 (d, J=5.4 Hz, 1H) , 5.84 (dc, J=9.8, 6.2 Hz, 1H), 5.72 (s, 2H), 4.62-4.48 (m, 1H), 4.15 (d, J =9.8 Hz, 1H), 3.90 (s, 3H), 2.06 (s, 3H), 1.26 (d, J=6.1 Hz, 3H), 0.93 (d, J =7.2Hz, 3H)
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -62.57 176 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₈ H ₂₉ Cl ₂ N ₂ O ₇ , 575.1352; found 575,1352 ¹ H NMR (300 MHz, CDCl ₃ ) δ 8.26 (d, J=5.4 Hz, 1H), 8.22 (d, J=7.8 Hz, 1H), 7.34-7.09 (m, 8H), 6.95 (d, J=5.4 Hz, 1H), 5.81-5.58 (m, 3H), 4.67-4.44 (m, 1H), 4, 04 (d, J=9.5 Hz, 1H), 3.90 (s, 3H), 2.06 (s, 3H), 1.24 (d, J=6.2 Hz, 3H), 1, 02 (d, J=7.1Hz, 3H)
¹³ C NMR (75 MHz, CDCl ₃ ) δ 172.19, 170.28, 162.91, 160.27, 145.71, 143.95, 142.32, 139.38, 139.28, 132.94 , 132.67, 129.49, 129.40, 129.01, 128.71, 109.64, 89.47, 72.65, 56.32, 56.22, 56.18, 48.05, 20 .89, 20.86, 19.12, 17.81 178 ... (Thin film) 3387, 2984, 1737, 1673, 1603, 1579, 1506, 1451, 1368, 1304, 1268, 1199, 1159, 1136, 1045, 1007, 969, 825, 779, 730, 730 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₇ H ₂₇ F ₂ N ₂ O ₆ , 513.1832; found 513,1833 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.35 (dd, J=4.5, 1.3 Hz, 1H), 8.15 (d, J=7.8 Hz, 1H), 7.52 (dd, J=8.4, 1.4 Hz, 1H), 7.42 (dd, J=8.4, 4.5 Hz, 1H), 7.33-7.14 (m, 4H), 7.05-6.86 (m, 4H), 5.82 (s, 2H), 5.72 (dc, J=9.7, 6.1 Hz, 1H), 4.59 (n, J= 7.3 Hz, 1H), 4.06 (d, J=9.7 Hz, 1H), 2.11 (s, 3H), 1.24 (d, J=6.2 Hz, 3H), 1 .01 (d, J=7.2 Hz, 3H)
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -115.57, -115.97 179 ... (Thin Film) 3380, 2985, 1737, 1674, 1603, 1578, 1507, 1473, 1455, 1366, 1312, 1274, 1222, 1200, 1158, 1104, 1043, 1003, 968, 9 10, 886, 824, 792, 728 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₉ H ₃₁ F ₂ N ₂ O ₇ , 557.2094; found 557,2089 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.23 (d, J=5.3 Hz, 1H), 8.18 (d, J=7.8 Hz, 1H), 7.23 (ddd, J =13.9, 6.9, 2.6 Hz, 4H), 7.05-6.84 (m, 5H), 5.78-5.66 (m, 3H), 4.56 (n, J =7.3 Hz, 1H), 4.12 (c, J=7.0 Hz, 2H), 4.05 (d, J=9.7 Hz, 1H), 2.06 (s, 3H), 1.47 (t, J=7.0 Hz, 3H), 1.24 (d, J=6.2 Hz, 3H), 1.00 (d, J=7.2 Hz, 3H)
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -115.60, -115.98 180 ... (Thin Film) 3404, 2983, 1737, 1652, 1602, 1508, 1482, 1453, 1369, 1305, 1222, 1197, 1159, 1137, 1106, 1088, 1049, 1010, 976, 9 11, 828, 792, 759, 732 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₈ H ₂₈ F ₂ NO ₆ , 512.1879; found 512,1889 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.13 (dd, J=7.9, 1.8 Hz, 1H), 8.06 (d, J=6.9 Hz, 1H), 7.45 (ddd, J=8.5, 7.4, 1.8 Hz, 1H), 7.29-7.05 (m, 6H), 7.04-6.90 (m, 4H), 5.92 (d, J=6.4 Hz, 1H), 5.83 (d, J=6.4 Hz, 1H), 5.73 (dc, J=9.9, 6.2 Hz, 1H), 4 .57 (n, J=7.1 Hz, 1H), 4.06 (d, J=9.7 Hz, 1H), 2.14 (s, 3H), 1.25 (d, J=6, 0Hz, 3H), 1.00 (d, J=7.2Hz, 3H)
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -115.62, -116.01 181 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₄₀ H ₃₉ N ₂ O ₇ , 659.2752; found 659,2758 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.24 (t, J=7.7 Hz, 2H), 7.57-7.49 (m, 8H), 7.45-7.37 (m, 8H), 7.32 (dt, J=9.3, 5.8 Hz, 2H), 6.90 (d, J=5.4 Hz, 1H), 5.89 (dc, J=12 A, 6.1 Hz, 1H), 5.71 (s, 2H), 4.58 (p, J=7.3 Hz, lH), 4.16 (d, J=10.0 Hz, 1H), 3 .88 (s, 3H), 2.05 (s, 3H), 1.33 (d, J=6.1 Hz, 3H), 0.96 (d, J=7.2 Hz, 3H)
¹³ C NMR (101 MHz, CDCl ₃ ) δ 172.38, 170.26, 162.88, 160.23, 145.68, 143.94, 142.52, 140.73, 140.61, 140.52 140.23 139.89 139.63 128.74 128.71 128.55 127.55 127.26 127.17 126.99 126.96 109.50 89 .54, 73.27, 57.25, 56.15, 48.12, 20.87, 19.34, 17.79 182 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₉ H ₃₇ N ₂ O ₆ , 629.2646; found 629,2651 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.41 (d, J=5.1 Hz, 1H), 8.29 (d, J=5.4 Hz, 1H), 7.57-7.47 (m, 8H), 7.41 (dd, J=9.3, 6.0 Hz, 8H), 7.32 (dd, J=12.1, 7.1 Hz, 2H), 6.94 ( e, J=5.5 Hz, 1H), 5.88 (dc, J=12.3, 6.1 Hz, lH), 4.57 (p, J=7.2 Hz, 1H), 4, 15 (d, J=10.0 Hz, 1H), 3.87 (s, 3H), 2.38 (s, 3H), 1.31 (d, J=6.1 Hz, 3H), 0, 95 (d, J=7.1 Hz, 3H)
¹³ C NMR (101 MHz, CDCl ₃ ) δ 172.24, 168.91, 162.29, 159.40, 146.63, 141.52, 140.73, 140.62, 140.47, 140.23 , 139.88, 139.62, 137.45, 128.75, 128.71, 128.56, 127.54, 127.25, 127.16, 127.00, 126.96, 109.69, 73 .30, 57.22, 56.25, 47.90, 20.75, 19.31, 17.97 183 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₇ H ₂₇ F ₂ N ₂ O ₇ , 530.1813; found 530,1809 ¹ H NMR (500 MHz, CDCl ₃ ) δ 8.28 (d, J=5.4 Hz, 1H), 8.15 (t, J=5.6 Hz, 1H), 7.25-7.15 (m, 4H), 7.03-6.89 (m, 5H), 5.75-5.66 (m, 3H), 4.11 (dd, J=18.3, 5.7 Hz, 1H ), 4.04 (d, J=9.1 Hz, 1H), 3.92 (s, 3H), 3.89 (dd, J=18.3, 5.4 Hz, 1H), 2.06 (s, 3H), 1.24 (d, J=6.2Hz, 3H)
¹³ C NMR (126 MHz, CDCl ₃ ) δ 170.32, 169.11, 161.72 (d, J=246.0 Hz), 161.62 (d, J=245.4 Hz), 160.31 , 145.73, 144.02, 142.27, 136.67 (d, J=26.2 Hz), 129.72, 129.66, 115.68 (d, J=21.5 Hz), 115 .41 (d, J=22.1 Hz), 109.65, 89.48, 73.37, 56.16, 55.69, 41.33, 20.87
¹⁹ F NMR (471 MHz, CDCl ₃ ) δ -115.60 (m), -115.94 (m) 184 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₉ H ₃₁ F ₂ N ₂ O ₇ , 558.2121; found 558.2133 ¹ H NMR (500 MHz, CDCl ₃ ) δ 8.26 (d, J=5.4 Hz, 1H), 8.22 (d, J=8.4 Hz, 1H), 7.28-7.18 (m, 4H), 7.01-6.90 (m, 5H), 5.77-5.65 (m, 3H), 4.56 (ddd, J=8.4, 6.7, 5, 3 Hz, 1H), 4.05 (d, J=9.6 Hz, 1H), 3.91 (s, 3H), 2.06 (s, 3H), 1.63-1.52 (m, 1H), 1.40-1.29 (m, 1H), 1.23 (d, J=6.2 Hz, 3H), 0.61 (t, J=7.4 Hz, 3H)
¹³ C NMR (126 MHz, CDCl ₃ ) δ 171.56, 170.27, 163.06, 161.72 (d, J=246.0 Hz), 161.66 (d, J=245.2 Hz) , 160.32, 145.66, 144.03, 142.38, 136.92, 129.60 (d, J=10.6 Hz), 129.54 (d, J=10.4 Hz), 115 .63 (d, J=35.4 Hz), 115.46 (d, J=35.4 Hz), 109.55, 89.59, 73.22, 56.19, 56.02, 53.26 , 25.24, 20.87, 19.22, 9.16
¹⁹ F NMR (471 MHz, CDCl ₃ ) δ -115.59 - -115.70 (m), -116.06 (ddd, J=14.0, 8.7, 5.3 Hz) 185 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₀ H ₃₃ F ₂ N ₂ O ₇ , 572.2283; found 572,2286 ¹ H NMR (500 MHz, CDCl ₃ ) δ 8.29-8.21 (m, 2H), 7.29-7.14 (m, 4H), 7.00-6.88 (m, 5H), 5.85-5.51 (m, 3H), 4.55 (dd, J=9.3, 4.6 Hz, 1H), 4.05 (d, J=9.6 Hz, 1H), 3 .91 (s, 3H), 2.06 (s, 3H), 1.87-1.75 (m, 1H), 1.22 (d, J=6.2 Hz, 3H), 0.78 ( d, J=6.9 Hz, 3H), 0.58 (d, J=6.8 Hz, 3H)
¹³ C NMR (126 MHz, CDCl ₃ ) δ 171.17, 170.27, 163.21, 161.70 (d, J=246.1 Hz), 161.66 (d, J=245.3 Hz) , 160.38, 145.62, 144.11, 142.32, 136.98, 129.54, 129.54 (d, J=14.9 Hz), 115.63 (d, J=32.3 Hz), 115.46 (d, J=32.3 Hz), 109.54, 89.63, 73.25, 57.14, 56.19, 55.97, 31.09, 20.88, 19 .27, 19.10, 17.06
¹⁹ F NMR (471 MHz, CDCl ₃ ) δ -115.69 (ddd, J=13.8, 8.8, 5.5 Hz), -116.12 (ddd, J=13.8, 8.7 , 5.5 Hz) 186 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₁ H ₃₅ F ₂ N ₂ O ₇ , 585.2407; found 585,2409 ¹ H NMR (500 MHz, CDCl ₃ ) δ 8.25 (d, J=5.4 Hz, 1H), 8.07 (d, J=8.8 Hz, 1H), 7.28-7.18 (m, 4H), 7.01-6.91 (m, 5H), 5.74-5.66 (m, 3H), 4.57 (ddd, J=9.6, 8.7, 5, 1 Hz, lH), 4.04 (d, J=9.9 Hz, 1H), 3.90 (s, 3H), 2.06 (s, 3H), 1.41-1.31 (m, 1H), 1.23 (d, J=6.1 Hz, 3H), 1.22-1.17 (m, 1H), 1.04-0.96 (m, 1H), 0.79 (d , J=6.5Hz, 3H), 0.74 (d, J=6.6Hz, 3H)
¹³ C NMR (126 MHz, CDCl ₃ ) δ 172.38, 170.29, 163.06, 161.73 (d, J=245.7 Hz), 161.67 (d, J=245.4 Hz) , 160.35, 145.57, 144.14, 142.22, 137.17, 136.90, 129.57 (d, J=12.1 Hz), 129.50 (d, J=11.8 Hz), 115.64 (d, J=35.1 Hz), 115.47 (d, J=35.0 Hz), 109.55, 89.60, 73.08, 56.20, 56.19 , 50.69, 41.20, 24.56, 22.80, 21.63, 20.87, 19.19
¹⁹ F NMR (471 MHz, CDCl ₃ ) δ -115.66 (td, J=9.1, 4.7 Hz), -116.21 (ddd, J=13.9, 8.7, 5.3 Hz) 187 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₆ H ₂₅ F ₂ N ₂ O ₆ , 499.1675; found 499,1664 ¹ H NMR (500 MHz, CDCl ₃ ) δ 8.38-8.23 (m, 2H), 7.27-7.12 (m, 4H), 7.10-6.83 (m, 5H), 5.69 (dc, J=9.1, 6.2 Hz, 1H), 4.13-3.95 (m, 2H), 3.92 (s, 4H), 2.39 (s, 3H) , 1.23 (d, J=6.2 Hz, 3H)
¹³ C NMR (126 MHz, CDCl ₃ ) δ 168.98, 168.92, 162.91, 161.71 (d, J=245.8 Hz), 161.62 (d, J=245.4 Hz) , 159.51, 146.67, 141.23, 137.55, 136.79, 136.53 (d, J=3.4 Hz), 129.72 (d, J=2.9 Hz), 129 .65 (d, J=2.7 Hz), 115.67 (d, J=21.3 Hz), 115.40 (d, J=21.3 Hz), 109.89, 73.42, 56 .31, 55.71, 41.17, 20.73, 19.11
¹⁹ F NMR (471 MHz, CDCl ₃ ) δ -115.55 - -115.66 (m), -115.95 (tt, J=8.3, 4.0 Hz) 188 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₈ H ₂₉ F ₂ N ₂ O ₆ , 527.1988; found 527,1981 ¹ H NMR (500 MHz, CDCl ₃ ) δ 8.39 (s, 1H), 8.32 (d, J=5.5 Hz, 1H), 7.33-7.04 (m, 4H), 7 .06-6.86 (m, 5H), 5.70 (dc, J=9.4, 6.1 Hz, 1H), 4.54 (ddd, J=8.6, 6.5, 5, 4 Hz, 1H), 4.04 (d, J=9.4 Hz, 1H), 3.91 (s, 3H), 2.38 (s, 3H), 1.62-1.49 (m, 1H), 1.40-1.30 (m, 1H), 1.22 (d, J=6.1 Hz, 3H), 0.59 (t, J=7.4 Hz, 3H)
¹³ C NMR (126 MHz, CDCl ₃ ) δ 171.41, 168.90, 162.46, 161.71 (d, J=245.9 Hz), 161.66 (d, J=245.4 Hz) , 159.46, 146.63, 141.46, 137.48, 136.88, 129.63 (d, J=7.8 Hz), 129.53 (d, J=7.8 Hz), 115 .67 (d, J=21.3 Hz), 115.40 (d, J=21.1 Hz), 109.74, 73.25, 56.30, 55.96, 53.02, 25.34 , 20.76, 19.20, 9.04
¹⁹ F NMR (471 MHz, CDCl ₃ ) δ -115.62 - -115.72 (m), -116.07 (td, J=9.3, 8.9, 4.1 Hz). 189 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₉ H ₃₁ F ₂ N ₂ O ₆ , 541.2145; found 541,2143 ¹ H NMR (500 MHz, CDCl ₃ ) δ 8.35 (s, 1H), 8.31 (d, J=5.4 Hz, 1H), 7.35-7.16 (m, 4H), 7 .08-6.80 (m, 5H), 5.70 (dc, J=9.5, 6.1 Hz, 1H), 4.51 (dd, J=9.5, 4.7 Hz, 1H ), 4.04 (d, J=9.5 Hz, 1H), 3.91 (s, 3H), 2.38 (s, 3H), 1.89-1.68 (m, 1H), 1 .21 (d, J=6.3Hz, 3H), 0.76 (d, J=6.9Hz, 3H), 0.58 (d, J=6.9Hz, 3H)
¹³ C NMR (126 MHz, CDCl ₃ ) δ 171.01, 168.88, 162.63, 161.69 (d, J=245.9 Hz), 161.65 (d, J=244.8 Hz) , 159.46, 146.61, 141.54, 137.48, 136.97 (d, J=3.3 Hz), 136.88 (d, J=3.4 Hz), 129.65 (d , J=1.9 Hz), 129.52 (d, J=8.0 Hz), 115.66 (d, J=21.3 Hz), 115.41 (d, J=21.3 Hz) , 109.71, 73.25, 56.95, 56.30, 55.91, 20.77, 19.25, 18.99, 17.09
¹⁹ F NMR (471 MHz, CDCl ₃ ) δ -115.67 - -115.78 (m), -116.06 - -116.17 (m) 190 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₀ H ₃₃ F ₂ N ₂ O ₆ , 555.2301; found 555,2292 ¹ H NMR (500 MHz, CDCl ₃ ) δ 8.30 (d, J=5.5 Hz, 1H), 8.18 (d, J=8.2 Hz, 1H), 7.35-7.13 (m, 4H), 7.04-6.80 (m, 5H), 5.68 (dc, J=9.8, 6.2 Hz, 1H), 4.54 (td, J=9.2 , 5.2 Hz, 1H), 4.03 (d, J=9.7 Hz, 1H), 3.90 (s, 3H), 2.38 (s, 3H), 1.20 (dd, J =16.3, 6.1 Hz, 4H), 1.04 (ddd, J=13.9, 8.7, 5.2 Hz, 1H), 0.91-0.81 (m, 1H), 0.78 (d, J=6.4Hz, 3H), 0.73 (d, J=6.6Hz, 3H)
¹³ C NMR (126 MHz, CDCl ₃ ) δ 172.20, 168.87, 162.46, 161.71 (d, J=245.7 Hz), 161.66 (d, J=245.4 Hz) , 159.46, 146.57, 141.50, 137.48, 137.07 (d, J=3.3 Hz), 136.89 (d, J=3.3 Hz), 129.60 (d , J=8.0 Hz), 129.50 (d, J=8.0 Hz), 115.68 (d, J=21.3 Hz), 115.40 (d, J=21.3 Hz) , 109.71, 73.08, 56.23, 50.54, 24.54, 22.76, 21.71, 20.76, 19.16
¹⁹ F NMR (471 MHz, CDCl ₃ ) δ -115.59 - -115.77 (m), -116.14 - -116.29 (m) 191 ... (Thin Film) 3381, 2937, 1735, 1676, 1492, 1245, 1203, 1042 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₀ H ₃₅ N ₂ O ₉ , 567.2335; found 567.2337 ¹ H NMR (300 MHz, CDCl ₃ ) δ 8.32-8.19 (m, 2H), 7.47 (dd, J=7.7, 1.8 Hz, 1H), 7.23 (s, 1H), 7.24-7.04 (m, 2H), 6.93 (d, J=5.5 Hz, 1H), 6.93-6.77 (m, 3H), 6.78 (dd , J=8.3, 1.2 Hz, 1H), 5.95 (dc, J=9.9, 6.2 Hz, 1H), 5.78-5.66 (m, 2H), 5, 01 (d, J=9.8 Hz, 1H), 4.62-4.48 (m, 1H), 3.90 (s, 3H), 3.85 (s, 3H), 3.76 (s , 3H), 2.06 (s, 3H), 1.24 (d, J=6.2 Hz, 3H), 0.95 (d, J=7.2 Hz, 3H) 192 ... (Thin Film) 3378, 2938, 1737, 1675, 1583, 1504, 1488, 1202, 1041 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₀ H ₃₅ N ₂ O ₉ , 567.2341; found 567.2337 ¹ H NMR (300 MHz, CDCl ₃ ) δ 8.27 (d, J=5.4 Hz, 1H), 8.23 (d, J=7.8 Hz, 1H), 7.26-7.14 (m, 1H), 7.16 (t, J=7.9 Hz, 1H), 6.93 (d, J=5.4 Hz, 1H), 6.92-6.87 (m, 2H) , 6.87-6.80 (m, 2H), 6.73 (ddd, J=8.2, 2.6, 0.9 Hz, 1H), 6.69 (ddd, J=8.2, 2.6, 0.9 Hz, 1H), 5.79 (dc, J=9.7, 5.8 Hz, 1H), 5.73-5.69 (m, 2H), 4.71-4 .44 (m, 1H), 3.99 (d, J=10.2 Hz, 1H), 3.90 (s, 3H), 3.77 (s, 3H), 3.76 (s, 3H) , 2.06 (s, 3H), 1.25 (d, J=6.1 Hz, 3H), 0.94 (d, J=7.2 Hz, 3H) 193 ... (Thin Film) 3378, 2983, 1741, 1672, 1575, 1483, 1201, 1002 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₈ H ₂₇ Cl ₂ F ₂ N ₂ O ₈ , 627.1102; found 627,1107 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.24 (dt, J=5.4, 1.3 Hz, 1H), 7.99 (d, J=8.1 Hz, 1H), 7.81 (t, J=8.5 Hz, lH), 7.36 (t, J=8.5 Hz, 1H), 7.19-7.10 (m, 1H), 7.07-6.98 ( m, 1H), 6.99-6.86 (m, 3H), 6.14-6.04 (m, 1H), 5.70 (d, J=6.4 Hz, 1H), 5.64 (d, J=6.4 Hz, 1H), 4.66 (n, J=7.2 Hz, 1H), 3.92 (s, 3H), 3.82 (s, 1H), 2.07 (s, 3H), 1.35 (d, J=7.2Hz, 3H), 1.22 (d, J=6.9Hz, 3H) 194 ... (Thin Film) 3380, 2984, 1738, 1675, 1504, 1201, 1003 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₀ H ₃₂ F ₂ N ₂ O ₇ , 571.2257; found 571,225 ¹ H NMR (300 MHz, CDCl ₃ ) δ 8.27 (d, J=5.4 Hz, 1H), 8.23 (d, J=7.8 Hz, 1H), 7.15-7.02 (m, 2H), 7.00-6.84 (m, 5H), 5.76-5.63 (m, 3H), 4.66-4.49 (m, 1H), 3.97 (d , J=9.8 Hz, 1H), 3.91 (s, 3H), 2.20 (d, J=1.9 Hz, 3H), 2.18 (d, J=1.8 Hz, 3H ), 2.06 (s, 3H), 1.24 (d, J=6.2 Hz, 3H), 1.02 (d, J=7.2 Hz, 3H)
¹⁹ F NMR (471 MHz, CDCl ₃ ) δ -116.63 (t, J=9.5 Hz), -117.12 (t, J=9.5 Hz) 195 ... (Thin Film) 3377, 2983, 1739, 1675, 1501, 1202, 1050 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₀ H ₃₃ Cl ₂ N ₂ O ₇ , 603.1657; found 603,1659 ¹ H NMR (300 MHz, CDCl ₃ ) δ 8.27 (d, J=5.4 Hz, 1H), 8.23 (d, J=7.9 Hz, 1H), 7.25-7.20 (m, 2H), 7.17-7.02 (m, 4H), 6.94 (d, J=5.4 Hz, 1H), 5.75-5.62 (m, 3H), 4, 68-4.50 (m, 1H), 3.95 (d, J=9.9 Hz, 1H), 3.91 (s, 3H), 2.31 (s, 3H), 2.28 (s , 3H), 2.06 (s, 3H), 1.24 (d, J=6.1 Hz, 3H), 1.03 (d, J=7.2 Hz, 3H) 196 ... (Thin Film) 3379, 2987, 1741, 1673, 1507, 1486, 1453, 1203, 1002 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₈ H ₂₉ F ₂ N ₂ O ₈ , 559.1884; found 559,1886 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.26 (d, J=5.4 Hz, 1H), 8.13 (d, J=8.1 Hz, 1H), 7.85 (tt, J =7.6, 1.9 Hz, lH), 7.47 (tt, J=1.1, 1.8 Hz, 1H), 7.28-7.20 (m, 1H), 7.22- 7.11 (m, 2H), 7.09-6.99 (m, 1H), 7.01-6.79 (m, 3H), 6.29-6.20 (m, 1H), 5. 71 (d, J=6.4 Hz, 1H), 5.67 (d, J=6.4 Hz, 1H), 4.75-4.57 (m, 1H), 3.91 (s, 3H ), 3.48 (d, J=6.1 Hz, 1H), 2.07 (s, 3H), 1.34-1.21 (m, 6H) 197 ... (Thin Film) 3379, 3282, 2984, 2107, 1738, 1674, 1503, 1202, 1043, 1004 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₂ H ₃₁ N ₂ O ₇ , 555.2125; found 555,2126 ¹ H NMR (300 MHz, CDCl ₃ ) δ 8.27 (d, J=5.4 Hz, 1H), 8.21 (d, J=7.8 Hz, 1H), 7.46-7.34 (m, 5H), 7.26-7.15 (m, 3H), 6.94 (d, J=5.4 Hz, 1H), 5.87-5.68 (m, 3H), 4, 62-4.48 (m, 1H), 4.07 (d, J=9.8 Hz, 1H), 3.91 (s, 3H), 3.05 (s, 1H), 3.03 (s , 1H), 2.06 (s, 3H), 1.34-1.22 (m, 3H), 0.98 (d, J=7.2 Hz, 3H) 198 (Thin Film) 3379, 2964, 1736, 1675, 1505, 1202, 1042, 1003 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₂ H ₃₉ N ₂ O ₇ , 563.2753; found 563,2752 ¹ H NMR (300 MHz, CDCl ₃ ) δ 8.27 (d, J=5.4 Hz, 1H), 8.23 (d, J=7.8 Hz, 1H), 7.24-7.18 (m, 4H), 7.14-7.03 (m, 5H), 6.93 (d, J=5.5 Hz, 1H), 5.87-5.69 (m, 3H), 4, 53 (p, J=13 Hz, 1H), 3.99 (d, J=10.1 Hz, 1H), 3.90 (d, J=1.0 Hz, 3H), 2.68-2, 48 (m, 4H), 2.06 (d, J=1.1 Hz, 3H), 1.24 (d, J=7.1 Hz, 3H), 1.22-1.10 (m, 6H ), 0.88 (d, J=1.2 Hz, 2H) 199 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₈ H ₃₀ FN ₂ O ₇ , 525.2032; found 525,2045 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.27 (d, J=5.3 Hz, 1H), 8.21 (d, J=7.9 Hz, 1H), 7.31-7.22 (m, 5H), 7.21-7.12 (m, 1H), 7.00-6.81 (m, 3H), 5.81-5.74 (m, 1H), 5.72 (d , J=0.8 Hz, 2H), 4.54 (n, J=7.2 Hz, 1H), 4.05 (d, J=9.9 Hz, 1H), 3.90 (s, 3H ), 2.06 (s, 3H), 1.24 (d, J=6.2 Hz, 3H), 0.92 (d, J=7.2 Hz, 3H)
¹³ C NMR (126 MHz, CDCl ₃ ) δ 172.31, 170.28, 162.87, 161.70 (d, J=245.6 Hz), 160.25, 145.69, 143.97, 142 .50, 141.20, 137.03 (d, J=3.3 Hz), 129.60 (d, J=7.8 Hz), 128.59, 128.02, 126.80, 115.60 (d, J=21.3 Hz), 109.52, 89.55, 73.11, 57.04, 56.18, 48.05, 20.87, 19.18, 17.74 201 ... ... ESIMS m/z 661.1 ([M+H] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.26 (d, J=5.4 Hz, 1H), 7.89 (d, J=8.0 Hz, 1H), 7.56 (d, J =2.2 Hz, 1H), 7.48 (d, J=2.2 Hz, 1H), 7.34 (dd, J=8.5, 4.2 Hz, 2H), 7.18 (ddd , J=10.5, 8.4, 2.2 Hz, 2H), 6.97 (d, J=5.4 Hz, 1H), 5.79 (q, J=6.3 Hz, 1H) , 5.68 (d, J=6.3 Hz, 1H), 5.61 (d, J=6.4 Hz, 1H), 4.63-4.52 (m, 1H), 3.92 ( s, 3H), 3.55 (s, 1H), 2.07 (s, 3H), 1.27 (d, J=7.2 Hz, 3H), 1.18 (d, J=6.3 Hz, 3H)
¹³ C NMR (126 MHz, acetone-^,) 5 166.30, 165.13, 158.33, 155.10, 140.60, 139.16, 138.49, 137.43, 137.10, 127 .58, 126.60, 126.48, 125.21, 123.17, 122.62, 119.99, 119.77, 104.55, 84.15, 73.35, 69.04, 51.05 , 43.24, 26.40, 15.69, 9.20 202 ... ... ESIMS m/z 627.1 ([M] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.26 (d, J=5.4 Hz, 1H), 7.91 (d, J=8.0 Hz, 1H), 7.33-7.27 (m, 3H), 7.21 (dd, J=10.4, 2.1 Hz, 1H), 7.11 (dd, J=8.5, 2.2, 0.8 Hz, 1H), 7.06 (ddd, J=8.6, 2.1, 0.9 Hz, 1H), 6.97 (d, J=5.4 Hz, 1H), 5.80 (k, J=6, 3 Hz, 1H), 5.68 (d, J=6.3 Hz, 1H), 5.61 (d, J=6.3 Hz, 1H), 4.63-4.51 (m, 1H) , 3.92 (s, 3H), 3.54 (s, 1H), 2.07 (s, 3H), 1.25 (d, J=7.2 Hz, 3H), 1.18 (d, J=6.4Hz, 3H)
¹³ C NMR (126 MHz, CDCl ₃ ) δ 171.43, 170.32, 163.50, 160.30, 157.99 (d, J=249.5 Hz), 157.96 (d, J=249 .3 Hz), 145.76, 145.20 (d, J=5.8 Hz), 143.73, 143.09 (d, J=6.l Hz), 142.58, 130.53 (d , J=3.2 Hz), 122.14 (d, J=3.8 Hz), 121.85 (d, J=3.5 Hz), 120.23 (d, J=17.8 Hz) , 120.05 (d, J=17.8 Hz), 114.70 (d, J=22.5 Hz), 114.34 (d, J=23.0 Hz), 109.72, 89.34 , 78.60, 74.30, 56.24, 48.39, 30.94, 20.86, 17.51, 14.43 203 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₀ H ₃₃ Cl ₂ N ₂ O ₇ , 603.1659; found 603,1666 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.27 (d, J=5.4 Hz, 1H), 8.21 (d, J=7.8 Hz, 1H), 7.26-7.19 (m, 2H), 7.10 (dd, J=8.5, 2.2 Hz, 2H), 7.03 (dd, J=13.4, 8.2, 2.3 Hz, 2H), 6.94 (d, J=5.5 Hz, 1H), 5.77-5.62 (m, 3H), 4.56 (p, J=1.2 Hz, 1H), 3.95 (d , J=10.0 Hz, 1H), 3.91 (s, 3H), 2.33 (s, 3H), 2.31 (s, 3H), 2.06 (s, 3H), 1.23 (d, J=6.1Hz, 3H), 1.00 (d, J=1.2Hz, 3H)
¹³ C NMR (126 MHz, CDCl ₃ ) δ 172.30, 170.28, 162.90, 160.27, 145.70, 143.97, 142.42, 139.64, 139.47, 136.51 , 136.11, 133.06, 132.71, 130.74, 130.63, 129.42, 129.12, 126.63, 126.49, 109.57, 89.52, 72.78, 56 .44, 56.19, 48.06, 20.87, 20.17, 20.09, 19.19 17.82 204 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₇ H ₂₇ FN ₂ O ₆ , 495.1926; found 495,1920 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.40 (d, J=7.9 Hz, 1H), 8.32 (d, J=5.5 Hz, 1H), 7.30-7.22 (m, 6H), 7.19-7.13 (m, 1H), 7.01-6.93 (m, 3H), 5.76 (dc, J=9.8, 6.2 Hz, 1H ), 4.58-4.49 (m, 1H), 4.05 (d, J=9.9 Hz, 1H), 3.90 (s, 3H), 2.38 (s, 3H), 1 .23 (d, J=6.1 Hz, 3H), 0.90 (d, J=7.2 Hz, 3H)
¹³ C NMR (126 MHz, CDCl ₃ ) δ 172.19, 168.90, 162.27, 161.69 (d, J=245.6 Hz), 159.42, 146.64, 141.51, 141 .14, 137.46, 137.02 (d, J=3.2 Hz), 129.60 (d, J=7.8 Hz), 128.59, 128.04, 126.81, 115.59 (d, J=21.2 Hz), 109.72, 73.14, 56.99, 56.28, 47.81, 20.74, 19.15, 17.92 206 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₉ H ₃₁ Cl ₂ N ₂ O ₆ , 573.1554; found 573,1551 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.40 (s, 1H), 8.32 (d, J=5.4 Hz, 1H), 7.22 (dd, J=17.1, 8, 2 Hz, 2H), 7.09 (dd, J=1.2, 2.2 Hz, 2H), 7.06-6.96 (m, 3H), 5.69 (dc, J=9.9 , 6.2 Hz, 1H), 4.61-4.47 (m, 1H), 3.96-3.92 (m, 1H), 3.90 (s, 3H), 2.38 (s, 3H), 2.32 (s, 3H), 2.30 (s, 3H), 1.22 (d, J=6.2 Hz, 3H), 0.99 (d, J=1.2 Hz, 3H)
¹³ C NMR (126 MHz, CDCl ₃ ) δ 172.16, 168.91, 162.30, 159.45, 146.64, 141.45, 139.58, 137.47, 136.50, 136.10 , 133.05, 132.71, 130.73, 130.63, 129.41, 129.12, 126.64, 126.51, 109.76, 72.82, 56.34, 47.83, 20 .75, 20.16, 20.09, 19.16, 18.00 207 52-65 ... HRMS-FAB (m/z) ([M+H] ⁺ ) calculated for C ₃₀ H ₃₃ F ₂ N ₂ O ₆ , 555.2301; found 555,2311 ¹ H NMR (500 MHz, CDCl ₃ ) δ 8.30 (d, J=5.5 Hz, 1H), 8.29 (broad s, 1H), 7.26-7.18 (m, 4H) , 7.01-6.88 (m, 5H), 5.70 (dc, J=9.5, 6.1 Hz, 1H), 4.64-4.48 (m, 1H), 4.04 (d, J=9.5 Hz, 1H), 3.88 (s, 3H), 1.39 (s, 9H), 1.22 (d, J=6.l Hz, 3H), 0.99 (d, J=7.1Hz, 3H)
¹³ C NMR (126 MHz, CDCl ₃ ) δ 176.0, 172.3, 162.2, 161.7 (d, J=245.8 Hz), 161.6 (d, J=245.6 Hz) , 159.4, 146.5, 142.1, 137.8, 136.9, 136.8, 129.6 (d, J=8.0 Hz), 129.5 (d, J=7.8 Hz), 115.7 (d, J=21.3 Hz), 115.4 (d, J=21.3 Hz), 109.5, 73.0, 56.3, 56.1, 47.8 , 39.1, 27.2, 19.1, 18.1
¹⁹ F NMR (471 MHz, CDCl ₃ ) δ -115.7, -116.0 208 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₉ H ₃₁ F ₂ N ₂ O ₆ , 541.2145; found 541,2159 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.30 (d, J=5.4 Hz, 2H), 7.28-7.14 (m, 4H), 7.02-6.89 (m, 5H), 5.70 (dc, J=9.5, 6.2 Hz, 1H), 4.63-4.48 (m, 1H), 4.04 (d, J=9.5 Hz, 1H ), 3.87 (s, 3H), 2.93 (hept., J=7.0 Hz, 1H), 1.34 (d, J=7.0 Hz, 6H), 1.22 (d, J=6.2Hz, 3H), 0.98 (d, J=7.1Hz, 3H)
¹³ C NMR (126 MHz, CDCl ₃ ) δ 174.69, 172.21, 162.69, 162.61, 162.28, 160.74, 160.66, 159.43, 146.54, 141.81 , 137.65, 136.86, 136.84, 129.64, 129.57, 129.51, 115.76, 115.59, 115.46, 115.30, 109.61, 73.03, 56 .29, 56.07, 47.79, 33.94, 19.12, 18.80, 18.04 209 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₉ H ₃₁ F ₂ N ₂ O ₇ , 557.209; found 557,2094 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.45-8.25 (m, 2H), 7.30-7.15 (m, 4H), 7.05-6.86 (m, 5H), 5.71 (dtd, J=9.7, 7.3, 6.8, 5.5 Hz, 1H), 4.53 (tt, J=8.3, 6.6 Hz, 1H), 4, 04 (d, J=9.6Hz, 1H), 3.88 (d, J=1.2Hz, 3H), 3.80 (td, J=6.6, 1.2Hz, 2H), 3.39 (d, J=1.2 Hz, 3H), 2.97 (td, J=6.7, 1.3 Hz, 2H), 1.22 (dd, J=6.3, 1, 3Hz, 3H), 0.98 (dd, J=7.2, 1.3Hz, 3H)
¹³ C NMR (126 MHz, CDCl ₃ ) δ 172.13, 169.42, 162.70, 162.61, 162.25, 160.74, 160.66, 159.46, 146.69, 141.44 137.34, 136.87, 136.84, 136.81, 129.63, 129.56, 129.50, 115.77, 115.60, 115.47, 115.30, 109.78, 73 .06, 67.57, 58.76, 56.31, 56.08, 47.81, 34.62, 19.12, 17.99 210 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₉ H ₂₉ F ₂ N ₂ O ₆ , 539.1985; found 539,1988 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.33 (dd, J=19.6, 5.4 Hz, 2H), 7.25-7.16 (m, 4H), 7.03-6, 88 (m, 5H), 5.70 (dc, J=9.5, 6.2 Hz, 1H), 4.65-4.52 (m, 1H), 4.04 (d, J=9, 6 Hz, 1H), 3.90 (s, 3H), 1.95 (tt, J=8.0, 4.6 Hz, 1H), 1.25 (dd, J=4.6, 3.1 Hz, 2H), 1.22 (d, J=6.2 Hz, 3H), 1.05 (dt, J=8.1, 3.5 Hz, 2H), 0.98 (d, J=7 .2 Hz, 3H)
¹³ C NMR (126 MHz, CDCl ₃ ) δ 172.45, 172.20, 162.70, 162.61, 162.26, 160.74, 160.66, 159.50, 146.56, 141.80 137.45, 136.87, 136.85, 136.83, 129.64, 129.57, 129.50, 115.76, 115.59, 115.47, 115.30, 109.68, 73 .03, 56.31, 56.08, 47.75, 19.13, 18.09, 13.00, 9.27 211 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₀ H ₃₃ F ₂ N ₂ O ₇ , 571.2242; found 571,225 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.25 (t, J=6.2 Hz, 2H), 7.32-7.11 (m, 4H), 7.04-6.85 (m, 5H), 5.79-5.65 (m, 3H), 4.55 (n, J=7.3 Hz, 1H), 4.04 (d, J=9.7 Hz, 1H), 3, 87 (s, 3H), 2.53 (hept., J=7.0 Hz, 1H), 1.23 (d, J=6.2 Hz, 3H), 1.12 (d, J=7, 0Hz, 6H), 0.99 (d, J=7.2Hz, 3H)
¹³ C NMR (126 MHz, CDCl ₃ ) δ 176.25, 172.25, 162.88, 162.70, 162.60, 160.74, 160.65, 160.26, 145.54, 144.21 142.02 136.94 136.92 136.86 136.83 129.60 129.56 129.54 129.49 115.77 115.60 115.47 115 .30, 109.53, 89.88, 73.01, 56.13, 48.05, 33.85, 19.15, 18.66, 17.81 212 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₀ H ₃₃ F ₂ N ₂ O ₈ , 587.2199; found 587.2217 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.23 (dd, J=16.1, 6.6 Hz, 2H), 7.25-7.18 (m, 4H), 7.02-6, 89 (m, 5H), 5.82-5.66 (m, 3H), 4.54 (n, J=7.3 Hz, 1H), 4.08 (s, 2H), 4.04 (d , J=9.7 Hz, 1H), 3.89 (s, 3H), 3.58 (k, J=7.0 Hz, 2H), 1.25-1.20 (m, 6H), 0 .99 (d, J=7.2 Hz, 3H)
¹³ C NMR (126 MHz, CDCl ₃ ) δ 172.20, 170.05, 162.84, 162.70, 162.61, 160.75, 160.65, 160.21, 145.73, 143.95 142.23 136.95 136.92 136.85 136.83 129.60 129.56 129.54 129.50 115.78 115.61 115.47 115 .30, 109.70, 89.55, 73.04, 67.78, 67.17, 56.23, 56.14, 53.46, 48.04, 19.15, 17.81, 15.00 , 14.95 213 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₀ H ₃₃ F ₂ N ₂ O ₆ , 555.2301; found 555,2315 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.45-8.22 (m, 2H), 7.30-7.15 (m, 4H), 7.04-6.89 (m, 5H), 5.71 (dc, J=9.5, 6.2 Hz, 1H), 4.63-4.45 (m, 1H), 4.04 (d, J=9.6 Hz, 1H), 3 .89 (s, 3H), 2.68 (t, J=7.6 Hz, 2H), 1.76 (n, J=7.6 Hz, 2H), 1.54-1.37 (m, 2H), 1.22 (d, J=6.1 Hz, 3H), 1.06-0.88 (m, 6H)
¹³ C NMR (126 MHz, CDCl ₃ ) δ 172.17, 171.61, 162.70, 162.61, 162.31, 160.74, 160.66, 159.47, 146.56, 141.61 137.57, 136.87, 136.85, 136.82, 129.63, 129.57, 129.50, 115.76, 115.60, 115.47, 115.30, 109.69, 73 .05, 56.26, 56.08, 47.80, 33.64, 29.70, 26.61, 22.20, 19.12, 18.02, 13.76 214 ... (Thin Film) 3388, 2970, 2363, 2029, 1738, 1677, 1604, 1508, 1449, 1414, 1366, 1307, 1218, 1203, 1159, 1139, 1113, 1042, 1000, 970, 908, 831, 806, 793, 778, 731, 711, 682, 670, 663 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₇ H ₂₆ BrF ₂ N ₂ O ₆ , 593.0921; found 593.0925 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.28 (d, J=7.8 Hz, 1H), 8.17 (d, J=4.9 Hz, 1H), 7.68 (d, J =4.9 Hz, 1H), 7.30-7.16 (m, 4H), 7.05-6.90 (m, 3H), 5.81-5.69 (m, 3H), 4, 54 (p, J=7.3 Hz, 1H), 4.05 (d, J=9.8 Hz, 1H), 2.09 (s, 3H), 1.59 (s, 1H), 1, 31-1.21 (m, 3H), 1.00 (d, J=7.2 Hz, 3H) 215 ... (Thin Film) 3380, 2985, 2362, 1769, 1738, 1674, 1609, 1591, 1572, 1513, 1434, 1367, 1310, 1277, 1202, 1175, 1150, 1113, 1051, 1009, 952, 907, 825, 805, 731, 668, 657 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₇ H ₂₅ F ₄ N ₂ O ₆ , 549.1643; found 549,1655 ¹ H NMR (300 MHz, CDCl ₃ ) δ 8.38 (d, J=8.0 Hz, 1H), 8.32 (d, J=5.4 Hz, 1H), 7.18-6.88 (m, 7H), 5.64 (dc, J=9.5, 6.3 Hz, 1H), 4.64-4.47 (m, 1H), 4.00 (d, J=9.3 Hz, 1H), 3.91 (s, 3H), 2.39 (s, 3H), 1.23 (d, J=6.1 Hz, 3H), 1.09 (d, J=7.2 Hz, 3H)
¹⁹ F NMR (471 MHz, CDCl ₃ ) δ -136.31 (ddd, J=20.1, 11.2, 8.2 Hz), -136.74 (ddd, J=20.3, 11.3 , 7.8 Hz), -139.14 - -139.50 (m), -139.70 (dddd, J=21.4, 10.6, 7.7, 4.1 Hz) 216 ... (Thin Film) 3375, 2984, 2361, 2132, 1770, 1738, 1676, 1590, 1572, 1499, 1452, 1437, 1367, 1311, 1251, 1199, 1175, 1098, 1061, 1010, 952, 907, 828, 805, 782, 764, 733, 687, 668, 657, 651 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₇ H ₂₅ Cl ₂ F ₂ N ₂ O ₆ , 581.1052; found 581,1061 ¹ H NMR (300 MHz, CDCl ₃ ) δ 8.38 (d, J=8.3 Hz, 1H), 8.31 (d, J=5.4 Hz, 1H), 7.26 (ddd, J =11.5, 7.2, 2.1 Hz, 2H), 7.18-6.95 (m, 5H), 5.63 (dc, J=9.3, 6.1 Hz, 1H), 4.65-4.49 (m, 1H), 4.00 (d, J=9.4 Hz, 1H), 3.91 (s, 3H), 2.39 (s, 3H), 1.24 (d, J=6.2Hz, 3H), 1.09 (d, J=7.2Hz, 3H)
¹⁹ F NMR (471 MHz, CDCl ₃ ) δ -116.85 - -117.26 (m), -117.29 - -117.50 (m) 217 ... (Thin Film) 3383, 2983, 1771, 1736, 1676, 1591, 1572, 1503, 1451, 1437, 1366, 1311, 1277, 1237, 1201, 1176, 1119, 1099, 1051, 1009, 949, 907, 825, 805, 790, 733, 668, 657 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₉ H ₃₁ F ₂ N ₂ O ₆ , 541.2145; found 541,2156 ¹ H NMR (300 MHz, CDCl ₃ ) δ 8.40 (d, J=8.2 Hz, 1H), 8.32 (d, J=5.4 Hz, 1H), 7.14-6.96 (m, 5H), 6.96-6.81 (m, 2H), 5.68 (dc, J=9.9, 6.1 Hz, 1H), 4.53 (dt, J=8.2 , 7.1 Hz, 1H), 3.94 (d, J=10.0 Hz, 1H), 3.90 (s, 3H), 2.38 (s, 3H), 2.22 (dd, J =6.7, 1.9Hz, 6H), 1.21(d, J=6.1Hz, 3H), 0.98(d, J=7.1Hz, 3H)
¹⁹ F NMR (471 MHz, CDCl ₃ ) δ -119.90 - -120.14 (m), -120.50 - -120.65 (m) 218 ... (Thin Film) 3376, 2988, 2363, 1742, 1675, 1609, 1580, 1515, 1454, 1435, 1368, 1310, 1284, 1236, 1203, 1181, 1149, 1120, 1043, 1004, 970, 910, 873, 829, 754, 734 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₈ H ₂₇ F ₄ N ₂ O ₇ , 579.1749; found 579,1762 ¹ H NMR (300 MHz, CDCl ₃ ) δ 8.27 (d, J=5.4 Hz, 1H), 8.21 (d, J=7.8 Hz, 1H), 7.18-6.85 (m, 7H), 5.72 (s, 2H), 5.65 (dc, J=10.5, 6.2 Hz, 1H), 4.58 (n, J=7.3 Hz, 1H) , 4.01 (d, J=9.4 Hz, 1H), 3.91 (s, 3H), 2.07 (s, 3H), 1.25 (d, J=5.9 Hz, 3H) , 1.09 (d, J=7.2 Hz, 3H)
¹⁹ F NMR (471 MHz, CDCl ₃ ) δ -136.29 (ddd, J=20.1, 11.2, 8.0 Hz), -136.73 (ddd, J=20.1, 11.3 , 8.0 Hz), -139.16 - -139.43 (m), -139.64 - -139.84 (m) 219 ... (Thin Film) 3393, 2986, 2364, 1742, 1676, 1580, 1499, 1454, 1437, 1408, 1367, 1310, 1250, 1202, 1180, 1148, 1101, 1061, 1044, 1004, 972, 911, 829, 732, 720, 687 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₈ H ₂₇ Cl ₂ F ₂ N ₂ O ₇ , 611.1158; found 611,1169 ¹ H NMR (300 MHz, CDCl ₃ ) δ 8.27 (dd, J=5.4, 1.1 Hz, 1H), 8.21 (d, J=7.8 Hz, 1H), 7.35 -7.19 (m, 2H), 7.20-7.01 (m, 4H), 6.96 (dd, J=5.5, 1.1 Hz, 1H), 5.72 (d, J =1.1 Hz, 2H), 5.64 (dddd, J=11.6, 9.1, 5.3, 3.3 Hz, 1H), 4.65-4.51 (m, 1H), 4.01 (d, J=9.5 Hz, 1H), 3.92 (d, J=1.1 Hz, 3H), 2.07 (d, J=1.1 Hz, 3H), 1, 30-1.21 (m, 3H), 1.09 (dd, J=7.1, 1.1 Hz, 3H)
¹⁹ F NMR (471 MHz, CDCl ₃ ) δ -116.92 - -117.10 (m), -117.36 - -117.53 (m) 220 ... (Thin Film) 3375, 2986, 1738, 1675, 1579, 1501, 1452, 1437, 1366, 1310, 1275, 1237, 1202, 1180, 1151, 1118, 1101, 1043, 1003, 970, 909, 828, 785, 730 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₀ H ₃₃ F ₂ N ₂ O ₇ , 571.2250; found 571,2265 ¹ H NMR (300 MHz, CDCl ₃ ) δ 8.27 (d, J=5.4 Hz, 1H), 8.21 (d, J=7.8 Hz, 1H), 7.05 (td, J =9.7, 8.2, 4.2 Hz, 4H), 6.98-6.82 (m, 3H), 5.78-5.54 (m, 3H), 4.63-4.48 (m, 1H), 3.95 (d, J=10.1 Hz, 1H), 3.91 (s, 3H), 2.22 (dd, J=6.4, 2.0 Hz, 6H) , 2.06 (s, 3H), 1.23 (d, J=6.1 Hz, 3H), 0.99 (d, J=7.2 Hz, 3H)
¹⁹ F NMR (471 MHz, CDCl ₃ ) δ -120.03 (dt, J=9.7, 5.9 Hz), -120.57 (dd, j=8.8, 5.4 Hz) 221 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₈ H ₂₇ Cl ₄ N ₂ O ₇ , 643.0567; found 643.0578 ¹ H NMR (300 MHz, CDCl ₃ ) δ 8.27 (d, J=5.4 Hz, 1H), 8.20 (d, J=7.8 Hz, 1H), 7.42-7.29 (m, 4H), 7.12 (dd, J=8.3, 2.2 Hz, 1H), 7.08 (dd, J=8.3, 2.2 Hz, 1H), 6.95 ( e, J=5.4 Hz, 1H), 5.72 (s, 2H), 5.70-5.58 (m, 1H), 4.58 (n, J=7.2 Hz, 1H), 4.00 (d, J=9.5 Hz, 1H), 3.91 (s, 3H), 2.07 (s, 3H), 1.26 (d, J=6.2 Hz, 3H), 1.10 (d, J=7.2 Hz, 3H)
¹³ C NMR (126 MHz, CDCl ₃ ) δ 172.13, 170.29, 162.96, 160.28, 145.71, 144.01, 142.25, 140.34, 133.06, 132.72 , 131.62, 131.29, 130.94, 130.67, 130.34, 130.11, 127.32, 109.64, 89.50, 72.10, 56.20, 55.71, 48 .07, 20.88, 19.07, 17.85 222 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₈ H ₂₇ Cl ₂ F ₂ N ₂ O ₇ , 611.1158; found 611,1175 ¹ H NMR (300 MHz, CDCl ₃ ) δ 8.27 (d, J=5.4 Hz, 1H), 8.20 (d, J=7.8 Hz, 1H), 7.32 (td, J = 8.3, 7.6 Hz, 2H), 7.11-6.93 (m, 4H), 5.72 (d, J=0.5 Hz, 3H), 5.71-5.60 ( m, 1H), 4.67-4.51 (m, 1H), 4.03 (d, J=9.3 Hz, 1H), 3.91 (s, 3H), 2.07 (s, 3H ), 1.26 (d, J=6.2 Hz, 3H), 1.09 (d, J=7.2 Hz, 3H)
¹³ C NMR (126 MHz, CDCl ₃ ) δ 172.10, 170.29, 162.95, 160.29, 158.15 (d, J=250.2 Hz), 158.01 (d, J=249 .8 Hz), 145.70, 144.03, 142.24, 141.03 (d, J=6.5 Hz), 131.08, 130.80, 124.51 (d, J=3.5 Hz), 124.40 (d, J=3.6 Hz), 120.03 (d, J=17.6 Hz), 119.73 (d, J=17.7 Hz), 116.55 (d , J=21.8 Hz), 109.64, 89.51, 72.15, 56.20, 55.99, 48.05, 20.87, 19.03, 17.84 223 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₇ H ₂₅ Cl ₄ N ₂ O ₆ , 613.0461; found 613.0468 ¹ H NMR (300 MHz, CDCl ₃ ) δ 8.80 (d, J=6.6 Hz, 1H), 8.49 (d, J=6.8 Hz, 1H), 7.58 (d, J =6.6 Hz, 1H), 7.40-7.27 (m, 4H), 7.14-7.01 (m, 2H), 5.67-5.52 (m, 1H), 4, 61-4.46 (m, lH), 4.18 (s, 3H), 4.10 (d, J=9.9 Hz, 1H), 2.44 (s, 3H), 1.27 (dd , J=6.3, 3.1Hz, 6H)
¹³ C NMR (126 MHz, CDCl ₃ ) δ 174.00, 171.63, 170.13, 140.79, 140.20, 133.07, 132.34, 131.62, 130.97, 130.85 , 130.55, 130.04, 127.30, 126.71, 108.57, 72.40, 58.02, 55.48, 34.67, 18.65, 16.34 224 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₇ H ₂₅ Cl ₂ F ₂ N ₂ O ₆ , 581.1052; found 581,1059 ¹ H NMR (300 MHz, CDCl ₃ ) δ 8.88 (d, J=6.7 Hz, 1H), 8.49 (d, J=6.7 Hz, 1H), 7.67 (d, J =6.7 Hz, 1H), 7.38-7.28 (m, 2H), 7.09-6.95 (m, 4H), 5.68-5.49 (m, 1H), 4, 59-4.48 (m, 1H), 4.21 (s, 3H), 4.12 (d, J=9.8 Hz, 1H), 2.44 (s, 3H), 1.31-1 .24 (m, 6H)
¹³ C NMR (126 MHz, CDCl ₃ ) δ 174.30, 171.60, 170.11, 157.88 (d, J=307.7 Hz), 141.43 (d, J=6.1 Hz) , 140.87 (d, J=6.2 Hz), 131.11, 130.71, 124.43, 123.96 (d, J=3.6 Hz), 120.02 (d, J=17 .7 Hz), 119.27 (d, J=17.3 Hz), 116.85 (d, J=21.3 Hz), 116.32 (d, J=21.5 Hz), 108.58 , 72.61, 58.04, 55.77, 50.35, 31.59, 18.66, 16.35
¹⁹ F NMR (471 MHz, CDCl ₃ ) δ -113.83 - -113.93 (m), -114.77 (t, J=8.7 Hz) 225 ... ... HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₈ H ₂₉ F ₂ N ₂ O ₇ , 543.1937; found 543,1949 ¹ H NMR (300 MHz, CDCl ₃ ) δ 8.27 (d, J=5.4 Hz, 1H), 8.13 (d, J=7.8 Hz, 1H), 7.25-7.14 (m, 4H), 6.93 (dddd, J=18.3, 8.7, 6.6, 2.1 Hz, 5H), 5.75-5.61 (m, 3H), 4.64 -4.42(m, 1H), 4.05(d, J=8.9Hz, 1H), 3.91(s, 3H), 2.05(s, 3H), 1.31(d, J=7.1Hz, 3H), 1.21(d, J=6.2Hz, 3H)
¹³ C NMR (126 MHz, CDCl ₃ ) δ 171.93, 170.30, 162.76, 162.66, 160.62, 160.36, 145.64, 144.15, 142.26, 136.92 , 136.54, 129.80, 129.74, 129.69, 129.62, 115.71, 115.54, 115.42, 115.25, 109.59, 89.62, 73.10, 56 .21, 55.59, 48.03, 20.86, 18.95, 18.06 226 ... (Thin Film) 3375, 2982, 1704, 1623, 1527, 1448, 1367, 1346, 1239, 1215, 1165, 1117, 1094, 1043, 863, 803, 786, 729, 679 HRMS-ESI (m/z) [M+Na] ⁺ calculated for C ₂₃ H ₂₃ F ₆ NNaO ₄ , 514.1423; found 514,1428 ¹ H NMR (400 MHz, CDCl ₃ ) δ 6.95-6.77 (m, 4H), 5.57 (dc, J=9.0, 6.2 Hz, 1H), 4.91 (d, J=7.8 Hz, 1H), 4.27-4.13 (m, 1H), 3.93 (d, J=9.0 Hz, 1H), 1.42 (s, 9H), 1, 24 (d, J=6.2Hz, 3H), 1.00 (d, J=7.2Hz, 3H)
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -132.38 (d, J=20.6 Hz), -132.83 (d, J=20.6 Hz), -160.90 (t, J= 20.5Hz), -161.25 (t, J=20.6Hz) 227 ... (Thin Film) 2939, 2031, 1744, 1620, 1526, 1447, 1345, 1234, 1217, 1118, 1041, 1005, 872, 826, 802, 752, 729, 707, 680, 666, 65 9 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₁₈ H ₁₆ F ₆ NO ₂ , 392.1080; found 392,1083 ¹ H NMR (400 MHz, methanol-d ₄ ) δ 7.36-7.17 (m, 4H), 5.83 (dc, J=10.0, 6.1 Hz, 1H), 4.26 ( d, J=10.1 Hz, 1H), 4.00 (c, J=7.2 Hz, 1H), 3.31 (n, J=1.7 Hz, 3H), 1.28 (d, J=6.2Hz, 3H), 1.08 (d, J=7.2Hz, 3H)
¹⁹ F NMR (376 MHz, methanol-d ₄ ) δ -137.08 (d, J=20.0 Hz), -137.39 (d, J=19.9 Hz), -166.29 (t, J=19.9Hz), -166.61 (t, J=19.9Hz) 228 ... (Thin Film) 3373, 2942, 1738, 1649, 1622, 1577, 1525, 1481, 1446, 1344, 1262, 1239, 1214, 1148, 1117, 1094, 1040, 984, 954, 90 9, 849, 801, 727, 678 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₅ H ₂₁ F ₆ N ₂ O ₅ , 543.1349; found 543,1362 ¹ H NMR (400 MHz, CDCl ₃ ) δ 11.93 (s, 1H), 8.29 (d, J=7.9 Hz, 1H), 7.98 (d, J=5.2 Hz, 1H ), 6.94-6.77 (m, 5H), 5.58 (dc, J=9.0, 6.2 Hz, 1H), 4.65-4.49 (m, 1H), 3, 94 (d, J=5.5Hz, 4H), 1.25 (dd, J=9.4, 6.7Hz, 6H)
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -132.34 (d, J=20.7 Hz), -132.74 (d, J=20.5 Hz), -160.82 (t, J= 20.5Hz), -161.08 (t, J=20.5Hz) 229 ... (Thin Film) 3384, 2985, 1770, 1741, 1676, 1622, 1592, 1572, 1527, 1447, 1368, 1345, 1312, 1237, 1199, 1176, 1117, 1095, 1042, 1010, 954, 909, 846, 828, 803, 729, 680 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₇ H ₂₃ F ₆ N ₂ O ₆ , 585.1455; found 585,1464 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.37 (d, J=7.6 Hz, 1H), 8.32 (d, J=5.4 Hz, 1H), 7.01 (d, J =5.5 Hz, 1H), 6.88 (dd, J=8.1, 6.3 Hz, 2H), 6.82 (dd, J=8.1, 6.2 Hz, 2H), 5 .56 (dc, J=8.7, 6.2 Hz, 1H), 4.65-4.50 (m, 1H), 3.94 (d, J=8.8 Hz, 1H), 3, 91 (s, 3H), 2.38 (s, 3H), 1.24 (d, J=6.2 Hz, 3H), 1.18 (d, J=7.2 Hz, 3H)
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -132.51 (d, J=20.5 Hz), -132.94 (d, J=20.4 Hz), -161.06 (t, J= 20.5Hz), -161.30 (t, J=20.6Hz) 230 ... (Thin Film) 3384, 2987, 1743, 1675, 1622, 1579, 1526, 1506, 1447, 1366, 1344, 1311, 1237, 1201, 1180, 1149, 1117, 1101, 1040, 1003, 971, 911, 830, 803, 728, 679 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₈ H ₂₅ F ₆ N ₂ O ₇ , 615.1560; found 615,1570 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.27 (d, J=5.4 Hz, 1H), 8.20 (d, J=7.7 Hz, 1H), 6.96 (d, J =5.4 Hz, 1H), 6.90 (dd, J=8.2, 6.3 Hz, 2H), 6.84 (dd, J=8.0, 6.2 Hz, 2H), 5 .72 (d, J=1.0 Hz, 2H), 5.58 (dc, J=8.9, 6.2 Hz, 1H), 4.59 (n, J=7.3 Hz, 1H) , 3.96 (d, J=8.8 Hz, 1H), 3.92 (s, 3H), 2.07 (s, 3H), 1.26 (d, J=6.2 Hz, 3H) , 1.17 (d, J=7.3 Hz, 3H)
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -132.49 (d, J=20.7 Hz), -132.92 (d, J=20.6 Hz), -161.02 (t, J= 20.6Hz), -161.33 (t, J=20.6Hz) 232 ... ... ESIMS m/z 320 ([M+H] ⁺ ) ... 233 ... ... ESIMS m/z 420 ([M+H] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.21 (ddd, J=11.8, 8.4, 5.2 Hz, 4H), 6.98 (td, J=8.6, 5.6 Hz, 4H), 5.67 (dc, J=9.2, 6.2 Hz, 1H), 4.80 (d, J=7.8 Hz, 1H), 4.06 (dd, J=21 .8, 8.4 Hz, 2H), 1.43 (s, 9H), 1.18 (dd, J=12.5, 6.7 Hz, 6H)
¹³ C NMR (126 MHz, CDCl ₃ ) δ 172.42, 162.70, 162.62, 160.74, 160.67, 136.89, 136.87, 129.74, 129.67, 129.61 , 115.76, 115.59, 115.47, 115.30, 79.79, 72.77, 55.76, 49.40, 30.93, 28.30, 19.00, 18.30 conn. no. Reg. ID MP (°C) IR (cm ^-1 ) MASS NMR ( ^1H , ^13C , ^19F ) 234

(Thin Film) 3367, 2979, 1708, 1495, 1162, 1049, 731 HRMS-ESI (m/z) ([M+Na] ⁺ ) calculated for C ₂₅ H ₃₁ F ₂ NNaO ₄ , 470.2113; found 470,2110 ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.25-7.17 (m, 1H), 7.14 (dd, J=8.4, 5.8 Hz, 1H), 6.91-6, 76 (m, 4H), 5.60 (dc, J=9.8, 6.2 Hz, 1H), 4.94 (d, J=8.0 Hz, 1H), 4.42 (d, J =9.8 Hz, 1H), 4.12 (cd, J=7.2, 2.5 Hz, 1H), 2.37 (s, 3H), 2.32 (s, 3H), 1.42 (s, 9H), 1.29 (d, J=6.1 Hz, 3H), 0.88 (d, J=7.2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -116.52, -117.01. 235

(Thin Film) 3440, 2963, 1708, 1365, 1164, 1051, 908, 731 HRMS-ESI (m/z) ([M+Na] ⁺ ) calculated for C ₃₁ H ₄₅ NNaO ₄ , 518.3241; found 518.3245 ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.33-7.17 (m, 8H), 5.77 (dc, J=10.3, 6.1 Hz, 1H), 4.97 (d, J=7.9 Hz, 1H), 4.10 (dc, J=14.6, 7.2 Hz, 1H), 3.95 (d, J=10.3 Hz, 1H), 1.41 ( s, 9H), 1.26 (s, 9H), 1.25-1.20 (m, 12H), 0.64 (d, J=7.2 Hz, 3H).
¹³ C NMR (101 MHz, CDCl ₃ ) δ 172.88, 154.92, 149.54, 149.34, 138.80, 138.25, 127.65, 127.61, 125.59, 125.29 , 79.54, 73.50, 57.27, 49.13, 34.34, 34.29, 31.30, 28.31, 19.36, 17.73. 236

(Thin Film) 3373, 2960, 1711, 1163, 1050, 731 HRMS-ESI (m/z) ([M+Na] ⁺ ) calculated for C ₂₉ H ₄₁ NNaO ₄ , 490.2928; found 490,2931 ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.24-7.17 (m, 4H), 7.16-7.05 (m, 4H), 5.76 (dc, J=10.2, 6 .1 Hz, 1H), 4.97 (d, J=7.9 Hz, 1H), 4.09 (dc, J=17.8, 7.3 Hz, 1H), 3.95 (d, J =10.3 Hz, 1H), 2.82 (dhept., J=9.4, 6.9 Hz, 2H), 1.41 (s, 9H), 1.22 (d, J=6.2 Hz, 3H), 1.17 (dd, J=11.6, 6.9 Hz, 12H), 0.67 (d, J=7.2 Hz, 3H).
¹³ C NMR (101 MHz, CDCl ₃ ) δ 172.87, 154.93, 147.27, 147.10, 139.20, 138.70, 127.91, 127.88, 126.75, 126.44 , 79.54, 73.45, 57.42, 49.16, 33.64, 33.60, 28.31, 24.00, 23.97, 23.91, 19.35, 17.79. 237

(Thin Film) 3364, 2976, 1712, 1501, 1450, 1162, 1052, 731 HRMS-ESI (m/z) ([M+Na] ⁺ ) calculated for C ₂₇ H ₃₇ NNaO ₄ , 462.2615; found 462,2623 ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.16-6.89 (m, 6H), 5.73 (dc, J=10.2, 6.1 Hz, 1H), 5.04-4, 90 (m, 1H), 4.19-4.02 (m, 1H), 3.88 (d, J=10.3 Hz, 1H), 2.17 (dd, J=10.4, 9, 0 Hz, 12H), 1.41 (s, 9H), 1.22 (d, J=6.1 Hz, 3H), 0.79 (d, J=7.1 Hz, 3H). 238

ESIMS m/z 442 ([M+H] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.23 (ddd, J=16.6, 8.5, 5.3 Hz, 4H), 6.97 (td, J=8.7, 2.2 Hz, 4H), 5.69 (dc, J=9.1, 6.2 Hz, 1H), 4.93 (d, J=7.3 Hz, 1H), 4.08 (dd, J=21 .8, 8.3 Hz, 2H), 1.43 (s, 9H), 1.18 (dd, J=13.2, 6.7 Hz, 6H).
¹³ C NMR (101 MHz, CDCl ₃ ) δ 172.40, 162.91, 162.84, 160.46, 160.40, 154.90, 136.97, 136.94, 136.66, 129.81 , 129.73, 129.69, 129.61, 129.53, 115.76, 115.71, 115.55, 115.50, 115.43, 115.22, 79.65, 77.45, 77 .13, 76.81, 72.71, 55.71, 49.44, 28.25, 18.92, 18.10. 239

ESIMS m/z 420 ([M+H] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) 5 7.23 (ddd, J=15.9, 8.7, 5.4 Hz, 4H), 6.97 (dtd, J=8.7, 6.4 , 2.1 Hz, 4H), 5.71 (dc, J=9.8, 6.1 Hz, 1H), 4.98 (d, J=7.8 Hz, lH), 4.14 (dc , J=14.9, 7.6 Hz, 1H), 4.03 (d, J=9.8 Hz, 1H), 1.42 (s, 9H), 1.22 (d, J=6, 1 Hz, 3H), 0.84 (d, J=7.2 Hz, 3H).
¹³ C NMR (101 MHz, CDCl ₃ ) δ 172.75, 162.96, 162.88, 160.51, 160.43, 154.94, 137.01, 136.97, 136.86, 136.82 , 129.58, 129.53, 129.51, 129.45, 115.80, 115.59, 115.49, 115.28, 79.71, 72.86, 56.20, 49.18, 28 .28, 19.17, 18.02. 240

(Thin Film) 3355, 2978, 1711, 1599, 1500, 1162, 954 HRMS-ESI (m/z) ([M+Na] ⁺ ) calculated for C ₂₅ H ₃₁ F ₂ NNaO ₆ , 502.2012; found 502,2021 ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.34 (dd, J=8.6, 6.7 Hz, 1H), 7.12 (dd, J=8.7, 6.7 Hz, 1H) , 6.64-6.44 (m, 4H), 5.85 (dc, J=9.5, 6.1 Hz, 1H), 4.96 (d, J=7.8 Hz, 1H), 4.81 (d, J=9.8 Hz, 1H), 4.23-4.02 (m, 1H), 3.82 (s, 3H), 3.74 (s, 3H), 1.42 (s, 9H), 1.20 (d, J=6.2 Hz, 3H), 0.88 (d, J=7.2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -113.46, -113.83. 241

ESIMS m/z 398 ([M+H] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.30-7.13 (m, 10H), 5.83 (q, J=6.4 Hz, 1H), 5.00 (d, J=5, 4 Hz, 1H), 4.26-4.12 (m, 1H), 1.73 (s, 3H), 1.41 (s, 9H), 1.15 (d, J=6.3 Hz, 3H), 0.98 (d, J=7.2 Hz, 3H).
¹³ C NMR (101 MHz, CDCl ₃ ) δ 172.77, 154.93, 146.56, 145.15, 128.16, 128.10, 127.92, 127.40, 126.28, 126.14 , 79.69, 75.78, 50.38, 49.39, 28.31, 23.89, 18.37, 15.98. 242

(Thin Film) 3375, 2980, 2934, 2229, 1739, 1708, 1605, 1504 ESIMS m/z 434 ([M+H] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.65-7.56 (m, 4H), 7.43-7.33 (m, 4H), 5.85-5.73 (m, 1H), 4.87 (d, J=7.9 Hz, 1H), 4.19 (dd, J=9.3, 2.7 Hz, 1H), 4.17-4.01 (m, 1H), 1 .42 (s, 9H), 1.25 (d, J=6.2 Hz, 3H), 0.85 (d, J=7.2 Hz, 3H). 243

(Thin Film) 3357, 2982, 1709, 1617, 1455 ESIMS m/z 520 ([M+H] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.56 (t, J=8.1 Hz, 4H), 7.44-7.36 (m, 4H), 5.89-5.76 (m, 1H), 4.89 (d, J=7.8 Hz, 1H), 4.19 (d, J=9.8 Hz, lH), 4.12 (t, J=7.5 Hz, 1H) , 1.41 (s, 9H), 1.26 (d, J=6.2 Hz, 3H), 0.79 (d, J=7.2 Hz, 3H). 244

(Thin Film) 3361, 2978, 1709, 1494, 1450, 1365, 1162, 1050, 1029, 731, 701 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₃ H ₃₀ NO ₄ , 384.2169; found 384.2169 Mixture of diastereomers 1:1. ¹ H NMR (500 MHz, CDCl ₃ ) δ 7.32-7.23 (m, 8H), 7.22-7.13 (m, 2H), 5.84-5.72 (m, 1H), 4.93 (d, J=7.9 Hz, 1H), 4.77 (d, J=6.2 Hz, 1H), 4.15-4.00 (m, 2H), 1.42 (s , 9H), 1.24 (d, J=6.3 Hz, 3H), 1.22 (d, J=6.0 Hz, 3H), 1.11 (d, J=7.2 Hz, 3H ), 0.76 (d, J=7.2 Hz, 3H).
¹³ C NMR (126 MHz, CDCl ₃ ) δ 172.83, 172.30, 154.93, 141.50, 141.26, 128.77, 128.73, 128.49, 128.46, 128.23 , 128.20, 128.08, 128.05, 126.90, 126.87, 126.66, 79.64, 73.11, 73.03, 57.97, 57.54, 49.46, 49 .17, 34.67, 28.32, 25.28, 20.70, 19.30, 19.10, 18.31, 18.00. 245

(Thin Film) 3374, 2977, 1711, 1592, 1489, 1247, 1163, 1029 HRMS-ESI (m/z) ([M+Na] ⁺ ) calculated for C ₂₅ H ₃₁ Cl ₂ NNaO ₆ , 534.1421; found 534,1427 ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.31 (d, J=8.2 Hz, 1H), 7.09 (d, J=8.1 Hz, 1H), 6.87 (dd, J =8.2, 2.0 Hz, 1H), 6.83 (dd, J=8.1, 2.0 Hz, 1H), 6.79 (dd, J=14.8, 2.0 Hz, 2H), 5.84 (dc, J=12.4, 6.2 Hz, 1H), 4.95 (d, J=7.3 Hz, 1H), 4.81 (d, J=9.7 Hz, 1H), 4.26-4.01(m, 1H), 3.82(s, 3H), 3.74(s, 3H), 1.42(s, 9H), 1.20(d , J=6.1Hz, 3H), 0.89 (d, J=7.2Hz, 3H) 246

(Thin Film) 3360, 2980, 1710, 1598, 1500, 1274, 1160, 1040, 990, 821 HRMS-ESI (m/z) ([M+Na] ⁺ ) calculated for C ₂₇ H ₃₅ F ₂ NNaO ₆ , 530.2325; found 530,2336 ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.30 (dd, J=8.5, 6.8 Hz, 1H), 7.14 (dd, J=8.5, 6.8 Hz, 1H) , 6.61-6.43 (m, 4H), 5.87 (dc, J=12.6, 6.3 Hz, 1H), 4.97 (d, J=6.9 Hz, 1H), 4.80 (d, J=10.1 Hz, 1H), 4.21-4.07 (m, 1H), 4.06-3.78 (m, 4H), 1.56-1.34 ( m, 15H), 1.21 (d, J=6.1 Hz, 3H), 0.90 (d, J=7.2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -113.72, -114.20. 247

(Thin Film) 3358, 2979, 1711, 1592, 1491, 1247, 1162, 1042 HRMS-ESI (m/z) ([M+Na] ⁺ ) calculated for C ₂₇ H ₃₅ Cl ₂ NNaO ₆ , 562.1734; found 562,1737 ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.27 (d, J=8.1 Hz, 1H), 7.10 (d, J=8.2 Hz, 1H), 6.84 (dd, J =5.6, 2.6 Hz, 1H), 6.81 (dd, J=8.2, 2.0 Hz, 1H), 6.75 (dd, J=14.9, 2.0 Hz, 2H), 5.86 (dc, J=12.2, 6.1 Hz, 1H), 4.98 (d, J=6.9 Hz, 1H), 4.80 (d, J=10.0 Hz, 1H), 4.23-4.07 (m, 1H), 4.07-3.75 (m, 4H), 1.52-1.34 (m, 15H), 1.21 (d, J=6.2 Hz, 3H), 0.91 (d, J=7.2 Hz, 3H). 248

(Thin Film) 3360, 2977, 1712, 1504, 1259, 1161, 1044 HRMS-ESI (m/z) ([M+Na] ⁺ ) calculated for C ₂₉ H ₄₁ NNaO ₆ , 522.2826; found 522,2819 ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.25 (d, J=7.7 Hz, 1H), 7.12 (d, J=7.8 Hz, 1H), 6.69-6.52 (m, 4H), 5.89 (dc, J=123, 6.1 Hz, 1H), 5.03 (d, J=6.1Uz, 1H), 4.88 (d, J=10.2 Hz, 1H), 4.10 (k, J=12.8, 9.8 Hz, 1H), 4.05-3.78 (m, 4H), 2.26 (s, 3H), 2.24 (s, 3H), 1.53-1.33 (m, 15H), 1.22 (d, J=6.2 Hz, 3H), 0.86 (d, J=1.1 Hz, 3H) . 249

ESIMS m/z 528 ([M+H] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.02-7.89 (m, 4H), 7.40-7.29 (m, 4H), 5.89-5.75 (m, 1H), 4.91 (d, J=8.0 Hz, 1H), 4.35 (q, J=7.1 Hz, 2H), 4.34 (q, J=7.1 Hz, 2H), 4, 18 (d, J=9.9 Hz, 1H), 4.16-4.03 (m, 1H), 1.41 (s, 9H), 1.37 (t, J=1.1 Hz, 6H ), 1.24 (d, J=6.2 Hz, 3H), 0.81 (d, J=1.2 Hz, 3H).
¹³ C NMR (101 MHz, CDCl ₃ ) δ 172.71, 172.69, 166.18, 166.10, 145.69, 145.36, 130.18, 129.91, 129.56, 129.31 , 128.25, 128.12, 72.36, 60.98, 60.95, 57.67, 28.29, 19.18, 18.09, 14.29, 14.28. 250

(Thin Film) 3378, 2979, 1707, 1592, 1453, 1134, 1050, 731 HRMS-ESI (m/z) ([M+Na] ⁺ ) calculated for C ₂₅ H ₃₁ F ₂ NNaO ₆ , 502.2012; found 502,2022 ¹ H NMR (400 MHz, CDCl ₃ ) δ 6.65-6.51 (m, 4H), 6.46 (tt, J=10.3, 2.3 Hz, 2H), 5.67 (dc, J=10.0, 6.1 Hz, 1H), 4.98 (d, J=7.9 Hz, lH), 4.14 (dd, J=10.5, 4.8 Hz, 1H), 3.92 (d, J=9.9 Hz, 1H), 3.76 (s, 3H), 3.75 (s, 3H), 1.42 (s, 9H), 1.24 (d, J =6.2 Hz, 3H), 0.88 (d, J=7.2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -110.64, -111.21. 251

(Thin Film) 3375, 2978, 1708, 1593, 1456, 1149, 1059, 729 HRMS-ESI (m/z) ([M+Na] ⁺ ) calculated for C ₂₇ H ₃₇ NNaO ₈ , 526.2411; found 526,2409 ¹ H NMR (400 MHz, CDCl ₃ ) δ 6.45 (dd, J=4.5, 2.2 Hz, 4H), 6.28 (dt, J=13.7, 2.2 Hz, 2H) , 5.73 (dc, J=10.3, 6.1 Hz, 1H), 5.00 (d, J=7.9 Hz, 1H), 4.12 (tt, J=7.1, 3 .3 Hz, 1H), 3.87 (d, J=10.4 Hz, 1H), 3.75 (s, 6H), 3.73 (s, 6H), 1.42 (s, 9H), 1.24 (d, J=6.1 Hz, 3H), 0.84 (d, J=7.2 Hz, 3H).
¹³ C NMR (101 MHz, CDCl ₃ ) δ 172.84, 160.97, 160.78, 154.94, 143.51, 143.22, 106.45, 106.20, 98.58, 98.44 , 79.63, 72.69, 58.27, 55.28, 55.26, 49.25, 28.31, 19.27, 18.07. 252

(Thin Film) 3370, 2978, 1708, 1594, 1454, 1292, 1153, 1051, 729 HRMS-ESI (m/z) ([M+Na] ⁺ ) calculated for C ₂₇ H ₃₇ NNaO ₆ , 494.2513; found 494,2510 ¹ H NMR (400 MHz, CDCl ₃ ) δ 6.69 (s, 2H), 6.66-6.62 (m, 2H), 6.54 (s, 1H), 6.50 (s, 1H) , 5.72 (dc, J=10.4, 6.1 Hz, 1H), 5.00 (d, J=7.9 Hz, 1H), 4.22-4.00 (m, 1H), 3.86 (d, J=10.4 Hz, 1H), 3.74 (s, 3H), 3.73 (s, 3H), 2.28 (s, 3H), 2.25 (s, 3H ), 1.41 (s, 9H), 1.22 (d, J=6.2 Hz, 3H), 0.80 (d, J=7.1 Hz, 3H).
¹³ C NMR (101 MHz, CDCl ₃ ) δ 172.85, 159.78, 159.65, 154.93, 142.79, 142.49, 139.72, 139.28, 121.29, 112.72 , 112.69, 111.34, 110.84, 79.59, 72.99, 57.93, 55.12, 55.11, 49.24, 28.32, 21.65, 21.58, 19 .31, 18.02. 253

(Thin Film) 3377, 2978, 1711, 1508, 1252, 1163, 1041, 732 HRMS-ESI (m/z) ([M+Na] ⁺ ) calculated for C ₂₇ H ₃₇ NNaO ₆ , 494.2513; found 494,2493 ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.00 (ddd, J=13.3, 7.6, 0.9 Hz, 2H), 6.85-6.68 (m, 4H), 5, 78 (dc, J=10.3, 6.1 Hz, 1H), 5.11-4.82 (m, 1H), 4.12 (cd, J=7.1, 2.3 Hz, 1H) , 3.94 (d, J=10.2 Hz, 1H), 3.79 (s, 3H), 3.78 (s, 3H), 2.14 (s, 3H), 2.12 (s, 3H), 1.41 (s, 9H), 1.24 (d, J=6.1 Hz, 3H), 0.80 (d, J=7.2 Hz, 3H).
¹³ C NMR (101 MHz, CDCl ₃ ) δ 172.87, 157.86, 157.65, 154.93, 140.45, 140.25, 130.75, 130.47, 125.22, 124.79 , 119.74, 119.69, 109.82, 109.77, 79.64, 73.09, 57.95, 55.27, 55.25, 49.29, 28.32, 19.35, 18 .06, 15.80, 15.75. 254

(Thin Film) 3377, 2979, 1706, 1513, 1274, 1161, 1025, 729 HRMS-ESI (m/z) ([M+Na] ⁺ ) calculated for C ₂₅ H ₃₁ F ₂ NNaO ₆ , 502.2012; found 502,2008 ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.06-6.92 (m, 4H), 6.88 (td, J=8.7, 4.6 Hz, 2H), 5.63 (dc, J=9.6, 6.2 Hz, 1H), 4.99 (d, J=7.9 Hz, 1H), 4.13 (p, J=6.9 Hz, 1H), 3.91 ( d, J=9.6 Hz, 1H), 3.84 (s, 3H), 3.83 (s, 3H), 1.42 (s, 9H), 1.22 (d, J=6.2 Hz, 3H), 0.90 (d, J=7.2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -134.14, -134.59. 255

(Thin Film) 3376, 2978, 1711, 1502, 1247, 1163, 1052, 730 HRMS-ESI (m/z) ([M+Na] ⁺ ) calculated for C ₂₇ H ₃₇ NNaO ₆ , 494.2513; found 494,2515 ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.05 (ddd, J=7.8, 4.8, 2.3 Hz, 2H), 7.01 (d, J=2.2 Hz, 2H) , 6.70 (t, J=8.8 Hz, 2H), 5.68 (dc, J=10.1, 6.1 Hz, 1H), 4.98 (d, J=7.9 Hz, 1H), 4.12 (ddp, J=11.8, 7.9, 4.3 Hz, 1H), 3.85 (d, J=10.2 Hz, 1H), 3.76 (s, 3H ), 3.74 (s, 3H), 2.16 (s, 3H), 2.14 (s, 3H), 1.41 (s, 9H), 1.21 (d, J=6.1 Hz , 3H), 0.82 (d, J=7.2 Hz, 3H).
¹³ C NMR (101 MHz, CDCl ₃ ) δ 172.87, 156.53, 156.36, 154.94, 133.77, 133.55, 130.40, 130.30, 126.81, 126.38 , 126.06, 125.86, 110.05, 109.91, 79.58, 73.47, 56.31, 55.32, 55.27, 49.28, 28.32, 19.34, 18 .15, 16.32, 16.24. 256

(Thin Film) 3355, 2978, 1712, 1497, 1223, 1161, 1047, 730 HRMS-ESI (m/z) ([M+Na] ⁺ ) calculated for C ₂₇ H ₃₇ NNaO ₈ , 526.2411; found 526,2405 ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.04 (d, J=3.0 Hz, 1H), 6.86 (d, J=3.0 Hz, 1H), 6.74 (dd, J =19.1, 8.9 Hz, 2H), 6.66 (ddd, J=9.1, 6.3, 3.0 Hz, 2H), 5.88 (dc, J=10.0, 6 .2 Hz, 1H), 5.03 (d, J=7.8 Hz, 1H), 4.91 (d, J=10.1 Hz, 1H), 4.12 (m, 1H), 3, 80 (s, 3H), 3.73 (s, 3H), 3.71 (s, 3H), 3.70 (s, 3H), 1.41 (s, 9H), 1.30-1.19 (m, 3H), 0.86 (d, J=7.2 Hz, 3H). 257

(Thin Film) 3364, 2978, 1710, 1497, 1245, 1160, 1045, 730 HRMS-ESI (m/z) ([M+Na] ⁺ ) calculated for C ₂₇ H ₃₇ NNaO ₆ , 494.2513; found 494,2507 ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.05 (d, J=8.4 Hz, 1H), 6.99 (d, J=8.3 Hz, 1H), 6.88 (d, J =2.7 Hz, 1H), 6.81 (d, J=2.7 Hz, 1H), 6.63 (ddd, J=15.9, 8.3, 2.7 Hz, 2H), 5 .63 (dc, J=10.0, 6.1 Hz, 1H), 4.99 (d, J=7.9 Hz, 1H), 4.43 (d, J=10.1 Hz, 1H) , 3.72 (s, 3H), 3.72 (s, 3H), 2.32 (s, 3H), 2.26 (s, 3H), 1.46-1.39 (m, 10H), 1.30 (d, J=6.2 Hz, 3H), 0.86 (d, J=7.2 Hz, 3H). 258

HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₇ H ₃₇ NO ₈ Na, 526.2411; found 526,2405 ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.08-6.91 (m, 3H), 6.89-6.82 (m, 1H), 6.76 (ddd, J=8.0, 3 .8, 1.7 Hz, 2H), 5.76-5.53 (m, 1H), 5.15-5.07 (m, 1H), 5.07-4.93 (m, 1H), 4.21-4.03(m, 1H), 3.90-3.80(m, 9H), 3.76-3.72(m, 3H), 1.47-1.37(m, 9H ), 1.24 (t, J=6.0 Hz, 3H), 1.14 (d, J=6.9 Hz, 1H), 0.86 (d, J=7.0 Hz, 2H).
¹³ C NMR (101 MHz, CDCl ₃ ) δ 172.73, 172.19, 152.83, 152.74, 147.49, 147.21, 135.15, 135.02, 134.77, 134.64 123.63, 123.58, 123.52, 120.98, 120.94, 120.51, 120.38, 110.86, 110.74, 110.67, 73.58, 60.35, 60 .29, 60.20, 55.65, 42.03, 41.98, 28.31, 18.90, 18.77, 18.52, 18.19. 259

(Thin Film) 3362, 2981, 1713, 1618, 1501, 1475, 1430, 1293, 1252, 1165, 1102, 1058, 951, 748 HRMS-ESI (m/z) ([M+Na] ⁺ ) calculated for C ₂₅ H ₂₉ F ₄ NO ₆ Na, 538.1823; found 538,1826 ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.09-7.02 (m, 1H), 6.88-6.74 (m, 3H), 5.70-5.59 (m, 1H), 4.95 (d, J=7.9 Hz, 1H), 4.85 (d, J=9.7 Hz, 1H), 4.22-4.07 (m, 1H), 3.97 (d , J=2.4 Hz, 3H), 3.86 (d, J=2.1 Hz, 3H), 1.42 (s, 9H), 1.23 (d, J=6.2 Hz, 3H ), 0.96 (d, J=7.2 Hz, 3H).
¹³ C NMR (126 MHz, CDCl ₃ ) δ 172.67, 154.91, 151.50, 151.26 (d, J=11.3 Hz), 149.47 (d, J=11.3 Hz) , 149.28 (d, J=11.5 Hz), 147.24, 147.18, 147.03, 146.97, 145.35, 145.24, 143.36, 143.25, 129.90 (d, J=3.5 Hz), 129.59, 123.09-122.78 (m), 122.38, 110.96-110.60 (m), 79.81, 72.19, 61 .23, 61.17, 49.21, 42.46, 28.29, 18.87, 18.29. 260

(Thin Film) 3382, 2977, 2930, 1715, 1501, 1453, 1365, 1249, 1167, 1049, 811, 734 HRMS-ESI (m/z) ([M+Na] ⁺ ) calculated for C ₂₇ H ₃₇ NO ₄ Na, 462.2615; found 462,2615 ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.07-6.84 (m, 6H), 5.64 (dc, J=11.9, 5.9 Hz, 1H), 4.96 (d, J=8.1 Hz, 1H), 4.44 (d, J=10.3 Hz, 1H), 4.18-4.02 (m, lH), 2.35 (s, 3H), 2, 29 (s, 3H), 2.27 (s, 3H), 2.25 (s, 3H), 1.42 (s, 9H), 1.27 (d, J=6.1 Hz, 3H), 0.82 (d, J=7.2 Hz, 3H).
¹³ C NMR (126 MHz, CDCl ₃ ) δ 172.97, 154.93, 139.18, 138.55, 135.43, 135.04, 133.58, 133.35, 130.57, 130.28 , 128.58, 127.87, 127.22, 126.90, 79.67, 74.72, 49.26, 47.36, 34.67, 28.32, 21.26, 21.22, 19 .77, 19.73, 18.86. 261

(Thin Film) 3364, 2977, 1713, 1499, 1452, 1365, 1209, 1164, 1049, 731 HRMS-ESI (m/z) ([M+Na] ⁺ ) calculated for C ₂₇ H ₃₇ NO ₄ Na, 462.2615; found 462,2614 ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.15 (d, J=8.5 Hz, 1H), 7.11 (d, J=8.5 Hz, 1H), 6.96-6.88 (m, 4H), 5.64 (dc, J=9.9, 6.1 Hz, 1H), 4.94 (d, J=7.9 Hz, 1H), 4.42 (d, J= 10.0 Hz, 1H), 4.17-4.05 (m, 1H), 2.34 (s, 3H), 2.30 (s, 3H), 2.25 (s, 3H), 2, 22 (s, 3H), 1.42 (s, 9H), 1.28 (d, J=6.2 Hz, 3H), 0.84 (d, J=7.1 Hz, 3H).
¹³ C NMR (126 MHz, CDCl ₃ ) δ 172.88, 154.95, 136.54, 136.39, 136.19, 136.07, 135.85, 135.52, 131.49, 131.16 , 127.74, 127.12, 126.82, 126.56, 79.63, 74.68, 49.24, 46.84, 34.67, 31.59, 28.32, 20.84, 20 .10, 20.06, 18.94. 262

(Thin Film) 3381, 2979, 1711, 1609, 1589, 1495, 1454, 1366, 1241, 1165, 1049, 810, 729 HRMS-ESI (m/z) ([M+Na] ⁺ ) calculated for C ₂₅ H ₃₁ F ₂ NO ₄ Na, 470.2113; found 470,2120 ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.11 (dd, J=8.4, 6.0 Hz, 1H), 7.07 (dd, J=8.5, 6.0 Hz, 1H) , 7.00 (dd, J=10.6, 2.6 Hz, 1H), 6.90 (dd, J=10.3, 2.7 Hz, 1H), 6.87-6.77 (m , 2H), 5.55 (dc, J=9.6, 6.2 Hz, 1H), 4.95 (d, J=7.2 Hz, 1H), 4.45 (dt, J=9, 6, 1.2 Hz, 1H), 4.20-4.08 (m, 1H), 2.34 (s, 3H), 2.28 (s, 3H), 1.42 (s, 9H), 1.31 (d, J=6.2 Hz, 3H), 0.89 (d, J=7.3 Hz, 3H).
¹³ C NMR (126 MHz, CDCl ₃ ) δ 172.77, 161.36 (d, J=243.9 Hz), 161.32 (d, J=243.5 Hz), 154.96, 140.69 (d, J=6.7 Hz), 140.10 (d, J=6.4 Hz), 132.38 (d, J=3.2 Hz), 132.07, 132.01, 131.69 (d, J=7.9 Hz), 114.83 (d, J=22.3 Hz), 114.34 (d, J=22.2 Hz), 113.67 (d, J=20.7 Hz), 113.35 (d, J=20.7 Hz), 79.79, 73.85, 49.16, 47.74, 34.67, 31.59, 28.31, 19.39, 19 .35, 18.82, 18.05. 263

(Thin film) 2978, 1710, 1497, 1454, 1366, 1249, 1209, 1160, 1036, 814, 728 HRMS-ESI (m/z) ([M+Na] ⁺ ) calculated for C ₂₅ H ₃₁ F ₂ NO ₆ , 502.2012; found 502,2011 ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.01-6.86 (m, 3H), 6.82 (dd, J=5.8, 3.1 Hz, 1H), 6.74-6, 64 (m, 2H), 5.82 (dc, J=12.0, 6.2 Hz, 1H), 4.97 (d, J=7.8 Hz, 1H), 4.67 (d, J =10.5 Hz, 1H), 4.21-4.09 (m, 1H), 3.74 (s, 6H), 1.42 (s, 9H), 1.29 (d, J=6, 2 Hz, 3H), 0.89 (d, J=7.3 Hz, 3H).
¹³ C NMR (126 MHz, CDCl ₃ ) δ 172.70, 156.13, 155.90, 155.74, 155.57, 154.90, 154.24, 154.00, 127.94 (d, J =15.8 Hz), 127.63 (d, J=16.2 Hz), 116.24 (d, J=24.9 Hz), 115.97 (d, J=24.8 Hz), 115 .14, 114.12, 113.16 (d, J=8.3 Hz), 113.03 (d, J=8.2 Hz), 79.69, 71.79, 55.70, 49.15 , 43.38, 34.66, 28.30, 19.00, 18.12. 264

(Thin Film) 2978, 2936, 1712, 1623, 1585, 1506, 1445, 1366, 1288, 1159, 1031, 950, 834, 731 HRMS-ESI (m/z) ([M+Na] ⁺ ) calculated for C ₂₅ H ₃₁ F ₂ NO ₆ Na, 502.2012; found 502,2016 ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.27 (t, J=8.6 Hz, 1H), 7.16 (t, J=8.5 Hz, 1H), 6.65-6.50 (m, 4H), 5.82-5.72 (m, 1H), 4.96 (d, J=7.9 Hz, 1H), 4.60 (d, J=10.2 Hz, 1H) , 4.21-4.09 (m, 1H), 3.75 (s, 3H), 3.74 (s, 3H), 1.42 (s, 9H), 1.26 (d, J=6 .1 Hz, 3H), 0.92 (d, J=7.3 Hz, 3H).
¹³ C NMR (126 MHz, CDCl ₃ ) δ 172.73, 161.24 (d, J=245.7 Hz), 161.01 (d, J=246.0 Hz), 159.73 (d, J = II. 1 Hz), 159.50 (d, J=11.3 Hz), 154.93, 129.86 (d, J=5.8 Hz), 129.31, 119.70 (d, J =14.6 Hz), 119.41 (d, J=15.1 Hz), 110.15 (d, J=2.9 Hz), 109.77 (d, J=3.0 Hz), 101 .81 (d, J=26.8 Hz), 79.67, 72.07, 55.51, 49.19, 41.73, 28.31, 19.01, 18.24. 265

(Thin Film) 2982, 1714, 1507, 1456, 1417, 1327, 1243, 1212, 1166, 1123, 1033, 860, 739 HRMS-ESI (m/z) ([M+Na] ⁺ ) calculated for C ₂₇ H ₃₁ F ₆ NO ₆ Na, 602,1948; found 602,1948 ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.53 (d, J=8.0 Hz, 1H), 7.31 (d, J=8.0 Hz, 1H), 7.16 (d, J =7.6Hz, 1H), 7.14-7.10(m, 1H), 7.01(dd, J=15.7, 1.7Hz, 2H), 6.01-5.91( m, 1H), 4.97 (d, J=9.7 Hz, 1H), 4.93 (d, J=8.0 Hz, 1H), 4.18-4.06 (m, 1H), 3.89 (s, 3H), 3.81 (s, 3H), 1.41 (s, 9H), 1.23 (d, J=6.2 Hz, 3H), 0.83 (d, J =7.2 Hz, 3H).
¹³ C NMR (126 MHz, CDCl ₃ ) δ 172.77, 157.43, 154.92, 132.51, 132.36, 130.03, 129.43, 125.01, 122.84, 117.27 (k, J=3.9 Hz), 116.99 (k, J=3.3 Hz), 107.64 (k, J=3.0 Hz), 107.44 (k, J=4.1 Hz), 79.75, 71.76, 55.70, 49.17, 28.29, 18.94, 18.11. 266

(Thin Film) 3355, 2961, 1712, 1493, 1366, 1266, 1160, 1095 HRMS-ESI (m/z) ([M+Na] ⁺ ) calculated for C ₂₇ H ₃₅ F ₂ NO ₆ Na, 530.2325; found 530,2331 ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.39 (dd, J=8.7, 5.6 Hz, 1H), 7.27-7.22 (m, 1H), 7.16-7, 05 (m, 2H), 6.98-6.89 (m, 2H), 5.58 (dc, J=8.8, 6.2 Hz, 1H), 4.95 (d, J=7, 4 Hz, 1H), 4.68 (d, J=9.1 Hz, 1H), 4.61 (d, J=12.4 Hz, 1H), 4.53 (d, J=12.5 Hz , 1H), 4.42 (d, J=12.3 Hz, 2H), 4.18-4.06 (m, 1H), 3.42 (s, 3H), 3.41 (s, 3H) , 1.42 (s, 9H), 1.27 (d, J=6.2 Hz, 3H), 0.90 (d, J=7.2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -115.52, -115.88. 267

(Thin Film) 3356, 2977, 1712, 1494, 1366, 1160, 1116, 1096 HRMS-ESI (m/z) ([M+Na] ⁺ ) calculated for C ₂₉ H ₃₉ F ₂ NO ₆ Na, 558.2638; found 558,2638 ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.40 (dd, J=8.7, 5.6 Hz, 1H), 7.24 (dd, J=8.7, 5.6 Hz, 1H) , 7.13 (t, J=3.2 Hz, lH), 7.10 (t, J=3.2 Hz, 1H), 6.96-6.88 (m, 2H), 5.59 ( dc, J=8.7, 6.2 Hz, 1H), 4.98 (d, J=7.5 Hz, 1H), 4.69 (d, J=8.9 Hz, 1H), 4, 65 (d, J=12.5 Hz, 1H), 4.59 (d, J=12.6 Hz, 1H), 4.46 (d, J=12.5 Hz, 1H), 4.45 ( d, J=12.6 Hz, 1H), 4.20-4.06 (m, 1H), 3.62-3.44 (m, 4H), 1.42 (s, 9H), 1.32 -1.18 (m, 9H), 0.91 (d, J=7.2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -115.64, -115.97. 268

(Thin Film) 3372, 2978, 2936, 2835, 1713, 1582, 1500, 1457, 1366, 1306, 1257, 1211, 1166, 1098, 1048, 910, 752, 734 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₇ H ₃₇ NO ₆ Na, 494.2513; found 494,2490 ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.07 (q, J=8.0 Hz, 4H), 6.93 (dd, J=7.7, 3.2 Hz, 2H), 6.85 (t, J=7.5 Hz, 2H), 6.74-6.62 (m, 4H), 5.65 (dcd, J=9.3, 6.1, 3.1 Hz, 2H), 4.96 (d, J=7.4 Hz, 1H), 4.81 (s, 1H), 4.60 (dd, J=9.9, 6.0 Hz, 2H), 4.09 (dt , J=15.3, 6.9 Hz, 2H), 3.79 (s, 6H), 3.77 (s, 3H), 3.76 (s, 3H), 2.27 (d, J= 7.5Hz, 6H), 2.20(s, 6H), 1.43(s, 9H), 1.42-1.38(m, 12H), 1.26(t, J=6.0 Hz, 6H), 0.83 (d, J=7.2 Hz, 3H). 269

(Thin Film) 3357, 2978, 1712, 1500, 1467, 1452, 1420, 1365, 1250, 1207, 1162, 1091, 1053, 1006, 909, 866, 765, 730 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₇ H ₃₇ NO ₆ Na, 494.2513; found 494,2509 ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.30 (dd, J=7.6, 1.4 Hz, 2H), 7.14 (d, J=7.7 Hz, 2H), 7.11 -6.99(m, 4H), 6.99-6.87(m, 4H), 5.73-5.49(m, 2H), 5.20(d, J=7.3Hz, 1H ), 5.14-4.98 (m, 3H), 4.11 (s, 2H), 3.81 (s, 3H), 3.76 (s, 3H), 3.74 (s, 3H) , 3.71 (s, 3H), 2.35-2.23 (m, 12H), 1.43 (d, J=12.5 Hz, 18H), 1.26 (dd, J=6.2 , 2.1 Hz, 6H), 1.09 (d, J=6.8 Hz, 3H), 0.82 (d, J=7.1 Hz, 3H). 270

(Thin film) 3364, 2976, 2935, 2836, 1711, 1608, 1585, 1504, 1453 ESIMS m/z 521 ([M+NH ₄ ] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.31 (d, J=8.5 Hz, 1H), 7.11 (d, J=8.4 Hz, 1H), 6.41 (dt, J =5.2, 2.6 Hz, 2H), 6.37 (dt, J=5.6, 2.7 Hz, 2H), 5.84 (dc, J=9.8, 6.2 Hz, 1H), 5.01 (d, J=7.9 Hz, 1H), 4.79 (d, J=9.9 Hz, 1H), 4.18-4.06 (m, 1H), 3, 81 (s, 3H), 3.74 (s, 6H), 3.73 (s, 3H), 1.42 (s, 9H), 1.20 (d, J=6.2 Hz, 3H), 0.88 (d, J=7.2 Hz, 3H). 271

(Thin film) 3365, 2977, 2934, 1712, 1611, 1504, 1452 ESIMS m/z 489 ([M+NH ₄ ] ⁺ ) ¹ H NMR (300 MHz, CDCl ₃ ) δ 7.28 (d, J=7.8 Hz, 1H), 7.13-7.03 (m, 1H), 6.69-6.56 (m, 4H), 5.86 (dc, J=9.8, 6.2 Hz, 1H), 5.01 (d, J=7.8 Hz, 1H), 4.88 (d, J=9.9 Hz, 1H), 4.20-3.98 (m, 1H), 3.81 (s, 3H), 3.73 (s, 3H), 2.27 (s, 3H), 2.26 (s , 3H), 1.41 (s, 9H), 1.21 (d, J=6.1 Hz, 3H), 0.85 (d, J=7.1 Hz, 3H). 272

(Thin Film) 3366, 2978, 2933, 2835, 1714, 1501, 1453 ESIMS m/z 489 ([M+NH ₄ ] ⁺ ) ¹ H NMR (300 MHz, CDCl ₃ ) δ 7.18 (d, J=2.1 Hz, 1H), 7.03 (d, J=2.2 Hz, 1H), 6.95-6.88 (m, 2H), 6.73 (d, J=8.3 Hz, 1H), 6.68 (d, J=8.3 Hz, 1H), 5.83 (dc, J=12.2, 6.1 Hz, 1H), 5.03 (d, J=7.9 Hz, 1H), 4.93 (d, J=10.3 Hz, 1H), 4.19-4.05 (m, 1H), 3.81 (s, 3H), 3.72 (s, 3H), 2.24 (s, 3H), 2.21 (s, 3H), 1.42 (d, J=0.6 Hz, 9H), 1.21 (d, J=6.1 Hz, 3H), 0.84 (d, J=7.2 Hz, 3H). 273

ESIMS m/z 480 ([M+H] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.05-6.93 (m, 2H), 6.91-6.75 (m, 4H), 5.71 (dc, J=10.1, 6 .2 Hz, 1H), 4.91 (d, J=1.9 Hz, 1H), 4.20-4.07 (m, 1H), 3.96 (d, J=10.0 Hz, 1H ), 3.86 (s, 3H), 3.85 (s, 3H), 1.42 (s, 9H), 1.23 (d, J=6.1 Hz, 3H), 0.86 (d , J=12 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -137.12, -137.69. 274

ESIMS m/z 472 ([M+H] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.22-7.04 (m, 2H), 6.77-6.56 (m, 4H), 5.60 (dc, J=9.8, 6 .1 Hz, 1H), 4.95 (d, J=7.9 Hz, 1H), 4.36 (d, J=10.0 Hz, 1H), 4.20-4.03 (m, 1H ), 3.75 (s, 3H), 3.73 (s, 3H), 2.35 (s, 3H), 2.31 (s, 3H), 1.42 (s, 9H), 1.27 (d, J=6.2 Hz, 3H), 0.87 (d, J=1.2 Hz, 3H). 275

ESIMS m/z 432 ([M+H] ⁺ ) 276

ESIMS m/z 432 ([M+H] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.35-7.28 (m, 2H), 7.25-7.20 (m, 2H), 7.20-7.09 (m, 2H), 6.65-6.51 (m, 2H), 5.81 (dc, J=10.0, 6.2 Hz, 1H), 4.92 (d, J=8.0 Hz, 1H), 4 .53 (d, J=10.1 Hz, 1H), 4.19-4.04 (m, 1H), 3.83 (s, 3H), 1.42 (s, 9H), 1.23 ( d, J=6.2 Hz, 3H), 0.78 (d, J=7.2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -113.26. 277

ESIMS m/z 416 ([M+H] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.33-7.20 (m, 5H), 7.19-7.10 (m, 1H), 6.92-6.81 (m, 2H), 5.75 (dc, J=10.3, 6.1 Hz, 1H), 4.91 (d, J=8.0 Hz, 1H), 4.26 (d, J=10.3 Hz, 1H ), 4.18-4.02 (m, 1H), 2.38 (s, 3H), 1.42 (s, 9H), 1.25 (d, J=6.1 Hz, 3H), 0 .79 (d, J=7.2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -116.70. 278

ESIMS m/z 432 ([M+H] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.32-7.12 (m, 6H), 6.59 (td, J=8.3, 2.6 Hz, 1H), 6.52 (dd, J=10.9, 2.5 Hz, 1H), 5.79 (dc, J=10.1, 6.1 Hz, 1H), 5.00 (d, J=8.2 Hz, 1H), 4.51 (d, J=10.2 Hz, 1H), 4.19-4.04 (m, 1H), 3.75 (s, 3H), 1.41 (s, 9H), 1.21 (d, J=6.1 Hz, 3H), 0.86 (d, J=7.2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -113.59. 279

ESIMS m/z 416 ([M+H] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.38-7.15 (m, 6H), 6.90-6.77 (m, 2H), 5.72 (dc, J=10.1, 6 .1 Hz, 1H), 4.97 (d, J=8.4 Hz, 1H), 4.23 (d, J=10.1 Hz, 1H), 4.19-4.03 (m, 1H ), 2.31 (s, 3H), 1.42 (s, 9H), 1.23 (d, J=6.1 Hz, 3H), 0.82 (d, J=7.2 Hz, 3H ).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -117.14. 280

ESIMS m/z 446 ([M+H] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.19 (d, J=8.0 Hz, 2H), 7.13 (dt, J=8.1, 6.5 Hz, 1H), 7.04 (d, J=7.9 Hz, 2H), 6.61-6.50 (m, 2H), 5.78 (dc, J=9.7, 6.1 Hz, 1H), 4.94 ( d, J=7.8 Hz, 1H), 4.49 (d, J=9.8 Hz, 1H), 3.82 (s, 3H), 2.26 (s, 3H), 1.42 ( s, 9H), 1.21 (d, J=6.2 Hz, 3H), 0.82 (d, J=7.2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -113.47. 281

ESIMS m/z 430 ([M+H] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.31-7.25 (m, 1H), 7.16-7.09 (m, 2H), 7.04 (d, J=7.8 Hz, 2H), 6.91-6.80 (m, 2H), 5.72 (dc, J=10.2, 6.2 Hz, 1H), 4.92 (d, J=8.0 Hz, 1H ), 4.22 (d, J=10.2 Hz, 1H), 4.18-4.02 (m, 1H), 2.37 (s, 3H), 2.25 (s, 3H), 1 .42 (s, 9H), 1.24 (d, J=6.1 Hz, 3H), 0.83 (d, J=7.2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -116.91. 282

ESIMS m/z 446 ([M+H] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.26 (dd, J=8.5, 6.5 Hz, 1H), 7.16 (d, J=8.1 Hz, 2H), 7.06 (d, J=8.0 Hz, 2H), 6.58 (td, J=8.3, 2.6 Hz, 1H), 6.52 (dd, J=10.9, 2.5 Hz, 1H), 5.77 (dc, J=10.1, 6.1 Hz, 1H), 5.01 (d, J=8.4 Hz, 1H), 4.48 (d, J=10.3 Hz, 1H), 4.19-4.04 (m, 1H), 3.76 (s, 3H), 2.27 (s, 3H), 1.41 (s, 9H), 1.21 (d , J=6.1 Hz, 3H), 0.85 (d, J=7.2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -113.81. 283

ESIMS m/z 430 ([M+H] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.31 (dd, J=8.6, 5.8 Hz, 1H), 7.14-7.04 (m, 4H), 6.87-6, 77 (m, 2H), 5.70 (dc, J=10.1, 6.1 Hz, 1H), 4.97 (d, J=7.8 Hz, 1H), 4.19 (d, J =10.3 Hz, 1H), 4.17-4.02 (m, 1H), 2.31 (s, 3H), 2.28 (s, 3H), 1.42 (s, 9H), 1 .22 (d, J=6.2 Hz, 3H), 0.81 (d, J=7.2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -117.35. 284

ESIMS m/z 450 ([M+H] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.35-7.22 (m, 2H), 7.12 (dd, J=8.4, 6.5 Hz, 1H), 6.98-6, 84 (m, 2H), 6.71-6.48 (m, 2H), 5.78 (dc, J=12.1, 6.3 Hz, 1H), 4.91 (d, J=8, 0 Hz, 1H), 4.49 (d, J=9.9 Hz, 1H), 4.25-4.02 (m, 1H), 3.82 (s, 3H), 1.42 (s, 9H), 1.22 (d, J=6.2 Hz, 3H), 0.84 (d, J=7.2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -112.92, -116.53. 285

ESIMS m/z 434 ([M+H] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.31-7.16 (m, 3H), 7.00-6.79 (m, 4H), 5.70 (dc, J=10.3, 6 .1 Hz, 1H), 4.89 (s, 1H), 4.25 (d, J=10.2 Hz, 1H), 4.18-4.04 (m, 1H), 2.36 (s , 3H), 1.42 (s, 9H), 1.25 (d, J=6.1 Hz, 3H), 0.87 (d, J=7.0 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -116.06, -116.38. 286

ESIMS m/z 450 ([M+H] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.25-7.19 (m, 3H), 6.99-6.90 (m, 2H), 6.60 (td, J=8.3, 2 .5 Hz, 1H), 6.54 (dd, J=10.9, 2.5 Hz, 1H), 5.74 (dc, J=11.9, 6.1 Hz, 1H), 4.94 (d, J=7.8 Hz, 1H), 4.48 (d, J=10.2 Hz, 1H), 4.19-4.05 (m, 1H), 3.77 (s, 3H) , 1.42 (s, 9H), 1.20 (d, J=6.2 Hz, 3H), 0.86 (d, J=7.3 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -113.32, -116.11. 287

ESIMS m/z 434 ([M+H] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.30 (dd, J=8.6, 5.7 Hz, 1H), 7.24-7.11 (m, 2H), 7.01-6, 93 (m, 2H), 6.92-6.69 (m, 2H), 5.67 (dc, J=10.0, 6.2 Hz, 1H), 4.92 (d, J=6, 4 Hz, 1H), 4.22 (d, J=10.0 Hz, 1H), 4.18-4.01 (m, 1H), 2.29 (s, 3H), 1.42 (s, 9H), 1.22 (d, J=6.2 Hz, 3H), 0.83 (d, J=7.2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -115.53, -116.86. 288

(Thin Film) 3364, 2978, 1709, 1600, 1496, 1161 HRMS-ESI (m/z) ([M+Na] ⁺ ) calculated for C ₂₅ H ₃₁ F ₂ NNaO ₅ , 486.2063; found 486,2063 ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.21 (dd, J=8.5, 6.6 Hz, lH), 7.16 (dd, J=8.5, 5.9 Hz, 1H) , 6.82 (tt, J=8.4, 4.1 Hz, 2H), 6.59 (td, J=8.2, 2.5 Hz, 1H), 6.53 (dd, J=10 .8, 2.4 Hz, 1H), 5.67 (dc, J=12.3, 6.1 Hz, 1H), 4.97 (d, J=6.5 Hz, 1H), 4.73 (d, J=10.2 Hz, 1H), 4.25-4.04 (m, 1H), 3.78 (s, 3H), 2.42 (s, 3H), 1.42 (s, 9H), 1.21 (d, J=6.1 Hz, 3H), 0.92 (d, J=7.2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -113.52, -116.98. 289

(Thin Film) 3364, 2979, 1710, 1601, 1501, 1162 HRMS-ESI (m/z) ([M+Na] ⁺ ) calculated for C ₂₄ H ₂₈ F ₃ NNaO ₅ , 490.1812; found 490,1809 ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.32-7.27 (m, 1H), 7.23-7.14 (m, 1H), 6.81-6.71 (m, 2H), 6.61 (td, J=8.3, 2.5 Hz, 1H), 6.54 (dd, J=10.8, 2.5 Hz, 1H), 5.79 (dc, J=11, 8, 6.1 Hz, 1H), 4.95 (d, J=7.1 Hz, 1H), 4.76 (d, J=10.1 Hz, 1H), 4.21-4.05 ( m, 1H), 3.76 (s, 3H), 1.42 (s, 9H), 1.23 (d, J=6.3 Hz, 3H), 0.90 (d, J=7.2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -112.15 (d, J=44.2 Hz), -112.17 (d, J=44.3 Hz), -112.91. 290

(Thin Film) 3365, 2979, 1709, 1497, 1450, 1160 HRMS-ESI (m/z) ([M+Na] ⁺ ) calculated for C ₂₅ H ₃₁ F ₂ NNaO ₅ , 486.2063; found 486,2067 ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.30 (dd, J=8.4, 6.2 Hz, 1H), 7.03 (dd, J=8.6, 6.6 Hz, 1H) , 6.80 (d, J=8.7 Hz, 2H), 6.58 (d, J=9.2 Hz, 2H), 5.65 (dc, J=9.9, 6.1 Hz, 1H), 4.93 (d, J=6.9 Hz, 1H), 4.73 (d, J=9.9 Hz, 1H), 4.18-4.04 (m, 1H), 3, 84 (s, 3H), 2.28 (s, 3H), 1.42 (s, 9H), 1.24 (d, J=6.2 Hz, 3H), 0.85 (d, J=7 .2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -112.94, -117.45. 291

(Thin film) 3364, 2980, 1711, 1499, 1163 HRMS-ESI (m/z) ([M+Na] ⁺ ) calculated for C ₂₄ H ₂₈ F ₃ NNaO ₄ , 474.1862; found 474,1863 ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.30 (dd, J=8.1, 5.8 Hz, 1H), 7.18-7.07 (m, 1H), 6.90-6, 75 (m, 4H), 5.67 (dc, J=11.7, 6.5 Hz, 1H), 4.92 (d, J=6.7 Hz, 1H), 4.61 (d, J =10.1 Hz, 1H), 4.19-3.95 (m, 1H), 2.29 (s, 3H), 1.42 (s, 9H), 1.27 (d, J=6, 3 Hz, 3H), 0.85 (d, J=7.2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -111.50 (d, J=7.3 Hz), -112.52 (d, J=7.1 Hz), -116.50. 292

(Thin Film) 3363, 2979, 2939, 2838, 1712, 1586, 1477 ¹ H NMR (400 MHz, CDCl ₃ ) for both diastereomers from a 1:1 mixture d 7.18-7.09 (m, 2H), 7.01-6.87 (m, 10H), 5.76-5 .58 (m, 2H), 5.03 (d, J=5.4 Hz, 1H), 5.01 (d, J=4.9 Hz, 1H), 5.01-4.90 (m, 2H), 4.20-4.06 (m, 2H), 3.92 (d, J=2.1 Hz, 3H), 3.89 (d, J=2.0 Hz, 3H), 3, 81 (d, J=1.9 Hz, 3H), 3.80 (d, J=1.9 Hz, 3H), 1.44 (s, 9H), 1.42 (s, 9H), 1, 25 (d, J=6.6 Hz, 3H), 1.23 (d, J=6.3 Hz, 3H), 1.17 (d, J=7.1 Hz, 3H), 0.90 ( e, J=7.2 Hz, 3H). 293

(Thin Film) 3364, 2980, 2839, 1712, 1495, 1455 ¹ H NMR (400 MHz, CDCl ₃ ) basic diastereomer of 2:1 mixture d 7.15 (dt, J=9.6, 3.0 Hz, 1H), 6.93 (td, J=8.8, 8 .2, 3.1 Hz, 1H), 6.89-6.81 (m, 2H), 6.80-6.68 (m, 2H), 5.84 (dd, J=9.6, 6 .2 Hz, 1H), 4.98 (s, 1H), 4.86 (d, J=9.2 Hz, 1H), 4.24-4.07 (m, 1H), 3.82 (s , 3H), 3.74 (s, 3H), 1.42 (s, 9H), 1.23 (d, J=6.3 Hz, 3H), 0.90 (d, J=7.2 Hz , 3H). 294

ESIMS m/z 412 ([M+H] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.19-7.10 (m, 2H), 7.10-7.07 (m, 4H), 7.03-6.98 (m, 1H), 6.98-6.92 (m, 1H), 5.76 (dc, J=10.3, 6.1 Hz, 1H), 4.94 (d, J=7.9 Hz, 1H), 4 .18-4.03 (m, 1H), 3.94 (d, J=10.3 Hz, 1H), 2.30 (s, 3H), 2.28 (s, 3H), 1.42 ( s, 9H), 1.22 (d, J=6.1 Hz, 3H), 0.76 (d, J=7.2 Hz, 3H).
¹³ C NMR (101 MHz, CDCl ₃ ) lost one aromatic C signal due to overlap d 172.84, 141.56, 141.27, 138.32, 137.91, 128.87, 128.87, 128, 60, 128.34, 127.62, 127.30, 125.06, 124.89, 73.20, 57.91, 53.39, 49.25, 28.31, 21.46, 21.42, 19.32, 18.01. 295

ESIMS m/z 416 ([M+H] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.32-7.21 (m, 5H), 7.21-7.15 (m, 1H), 6.86 (dd, J=8.0, 1 .7 Hz, 1H), 6.79 (dd, J=11.3, 1.6 Hz, 1H), 5.85-5.72 (m, 1H), 5.04-4.94 (m, 1H), 4.39 (d, J=10.1 Hz, 1H), 4.14 (n, J=7.4, 6.8 Hz, 1H), 2.26 (s, 3H), 1, 42 (s, 9H), 1.24 (d, J=6.1 Hz, 3H), 0.90-0.81 (m, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -118.88. 296

ESIMS m/z 434 ([M+H] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.28-7.17 (m, 3H), 6.99-6.93 (m, 2H), 6.88 (dd, J=8.0, 1 .7 Hz, 1H), 6.80 (dd, J=11.2, 1.6 Hz, 1H), 5.74 (dc, J=9.9, 6.2 Hz, 1H), 4.98 (d, J=7.9 Hz, 1H), 4.37 (d, J=10.0 Hz, 1H), 4.22-4.07 (m, 1H), 2.27 (s, 3H) , 1.42 (s, 9H), 1.23 (d, J=6.2 Hz, 3H), 0.88 (d, J=7.5 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -115.62, -118.85. 297

ESIMS m/z 430 ([M+H] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.22 (t, J=8.0 Hz, 1H), 7.19-7.13 (m, 2H), 7.07 (d, J=7, 9 Hz, 2H), 6.85 (dd, J=8.0, 1.8 Hz, 1H), 6.77 (dd, J=11.2, 1.6 Hz, 1H), 5.83- 5.69 (m, 1H), 5.03 (d, J=8.0 Hz, 1H), 4.35 (d, J=10.3 Hz, 1H), 4.19-4.05 (m , 1H), 2.27 (s, 3H), 2.24 (s, 3H), 1.41 (s, 9H), 1.23 (d, J=6.1 Hz, 3H), 0.86 (d, J=8.4 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -118.95. 298

ESIMS m/z 416 ([M+H] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.31-7.22 (m, 4H), 7.22-7.11 (m, 1H), 7.12-7.02 (m, 2H), 6.91 (dd, J=9.4, 8.2 Hz, 1H), 5.74 (dc, J=10.1, 6.2 Hz, 1H), 4.92 (d, J=7, 9 Hz, 1H), 4.17-4.04 (m, 1H), 3.97 (d, J=10.2 Hz, 1H), 2.23 (d, J=1.9 Hz, 3H) , 1.41 (s, 9H), 1.23 (d, J=6.2 Hz, 3H), 0.76 (d, J=7.2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -120.18. 299

ESIMS m/z 464 ([M+H] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.23 (dd, J=8.6, 6.6 Hz, 1H), 7.07-7.01 (m, 2H), 6.88 (t, J=9.3Hz, 1H), 6.60 (td, J=8.3, 2.6Hz, 1H), 6.54 (dd, J=10.9, 2.5Hz, 1H), 5.72 (dc, J=11.8, 6.0 Hz, 1H), 4.95 (d, J=8.0 Hz, 1H), 4.44 (d, J=10.3 Hz, 1H ), 4.19-4.07 (m, 1H), 3.78 (s, 3H), 2.22 (d, J=1.9 Hz, 3H), 1.42 (s, 9H), 1 .20 (d, J=6.1 Hz, 3H), 0.86 (d, J=7.2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -113.49, -120.41. 300

ESIMS m/z 448 ([M+H] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.24 (dd, J=9.6, 5.6 Hz, lH), 7.16 (t, J=7.9 Hz, 1H), 6.85 (dt, J=10.4, 2.4 Hz, 3H), 6.79 (dt, J=11.3, 1.1 Hz, 1H), 5.70 (dc, J=10.2, 6 .2 Hz, 1H), 4.99 (d, J=8.0 Hz, 1H), 4.61 (d, J=10.1 Hz, 1H), 4.22-4.09 (m, 1H ), 2.39 (s, 3H), 2.26 (s, 3H), 1.42 (s, 9H), 1.25 (d, J=6.1 Hz, 3H), 0.92 (d , J=7.2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -116.47, -118.10. 301

ESIMS m/z 452 ([M+H] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.30-7.21 (m, 2H), 6.92-6.85 (m, 1H), 6.85-6.74 (m, 3H), 5.84-5.73 (m, 1H), 4.97 (d, J=7.9 Hz, 1H), 4.68 (d, J=10.0 Hz, 1H), 4.22-4 .07 (m, 1H), 2.28 (s, 3H), 1.42 (s, 9H), 1.26 (d, J=6.2 Hz, 3H), 0.90 (d, J= 7.3 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -111.63 (d, J=7.5 Hz), -112.07 (d, J=7.0 Hz), -118.16. 302

(Thin Film) 3366, 2979, 2932, 1713, 1496, 1452, 1365, 1306, 1248, 1211, 1165, 1053, 699 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₄ H ₃₂ NO ₄ , 398.2326; found 398,2328 ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.29-7.21 (m, 4H), 7.19-7.13 (m, 3H), 7.09 (d, J=7.9 Hz, 2H), 5.77 (dc, J=10.3, 6.1 Hz, 1H), 4.92 (d, J=7.9 Hz, 1H), 4.17-4.04 (m, 1H ), 3.99 (d, J=10.3 Hz, 1H), 2.28 (s, 3H), 1.41 (s, 9H), 1.23 (d, J=6.1 Hz, 3H ), 0.75 (d, J=7.2 Hz, 3H).
¹³ C NMR (126 MHz, CDCl ₃ ) δ 172.83, 154.94, 141.81, 138.26, 136.50, 129.98, 129.46, 128.47, 127.93 (d, J =3.6Hz), 126.56, 120.94, 79.63, 73.17, 57.62, 49.18, 34.67, 28.31, 20.97, 19.30, 18.00 . 303

(Thin Film) 3371, 2978, 2931, 1712, 1495, 1451, 1365, 1165, 1051, 699 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₄ H ₃₂ NO ₄ , 398.2326; found 398,2324 ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.26 (d, J=4.5 Hz, 5H), 7.18 (d, J=7.9 Hz, 2H), 7.05 (d, J =7.9 Hz, 2H), 5.77 (dc, J=10.0, 6.2 Hz, 1H), 4.94 (d, J=7.9 Hz, 1H), 4.18-4 .05 (m, 1H), 3.99 (d, J=10.0 Hz, 1H), 2.26 (s, 3H), 1.42 (s, 9H), 1.22 (d, J= 6.2 Hz, 3H), 0.80 (d, J=7.2 Hz, 3H).
¹³ C NMR (126 MHz, CDCl ₃ ) δ 172.83, 154.94, 141.52, 138.41, 136.15, 129.12, 128.73, 128.21, 128.05, 127.95 , 126.79, 124.35, 79.63, 73.17, 57.47, 49.21, 34.67, 28.31, 20.94, 19.30, 18.08. 304

(Thin Film) 3371, 2979, 2932, 1712, 1508, 1452, 1366, 1222, 1160, 1053, 816 HRMS-ESI (m/z) ([M+Na] ⁺ ) calculated for C ₂₄ H ₃₀ FNO ₄ Na, 438.2051; found 438,2052 ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.25-7.20 (m, 2H), 7.15 (d, J=8.1 Hz, 2H), 7.07 (d, J=7, 9 Hz, 2H), 6.96 (t, J=8.7 Hz, 2H), 5.72 (dc, J=9.7, 6.2 Hz, 1H), 4.93 (d, J= 7.9 Hz, 1H), 4.17-4.06 (m, 1H), 3.99 (d, J=9.8 Hz, 1H), 2.27 (s, 3H), 1.42 ( s, 9H), 1.21 (d, J=6.2 Hz, 3H), 0.81 (d, J=7.2 Hz, 3H).
¹³ C NMR (126 MHz, CDCl ₃ ) δ 172.80, 161.65 (d, J=245.5 Hz), 154.94, 138.13, 137.32 (d, J=3.2 Hz) , 136.35, 129.52 (d, J=7.9 Hz), 129.22, 127.89, 126.12 (d, J=7.8 Hz), 115.56 (d, J=21 .3 Hz), 79.68, 73.01, 56.60, 49.19, 34.67, 31.59, 28.31, 20.95, 19.22, 18.07. 305

(Thin Film) 3371, 2979, 2933, 1710, 1509, 1452, 1366, 1222, 1160, 1051, 699 ESIMS m/z 402.2 ([M+H] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.31-7.23 (m, 7H), 6.98-6.92 (m, 2H), 5.75 (dc, J=10.0, 6 .2 Hz, 1H), 4.91 (d, J=7.8 Hz, 1H), 4.18-4.07 (m, 1H), 4.02 (d, J=10.0 Hz, 1H ), 1.42 (s, 9H), 1.23 (d, J=6.2 Hz, 3H), 0.83 (d, J=7.2 Hz, 3H).
¹³ C NMR (126 MHz, CDCl ₃ ) δ 172.80, 161.61 (d, J=245.2 Hz), 154.93, 141.02, 137.26 (d, J=3.4 Hz) , 129.55 (d, J=7.9 Hz), 128.86, 127.99, 127.05, 115.29 (d, J=21.2 Hz), 79.74, 73.05, 57 .10, 49.18, 34.67, 28.31, 19.29, 18.12. 306

(Thin Film) 3371, 2979, 2932, 1712, 1509, 1452, 1366, 1222, 1161, 1052, 815 ESIMS m/z 438.2 ([M+Na] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.26-7.21 (m, 2H), 7.14 (d, J=8.2 Hz, 2H), 7.09 (d, J=8, 1 Hz, 2H), 6.98-6.90 (m, 2H), 5.73 (dc, J=10.2, 6.1 Hz, 1H), 4.91 (d, J=8.0 Hz, 1H), 4.17-4.06 (m, 1H), 3.98 (d, J=10.2 Hz, 1H), 2.29 (s, 3H), 1.42 (s, 9H ), 1.22 (d, J=6.1 Hz, 3H), 0.82 (d, J=7.2 Hz, 3H).
¹³ C NMR (126 MHz, CDCl ₃ ) δ 172.80, 161.56 (d, J=245.0 Hz), 154.93, 138.04, 137.58 (d, J=3.3 Hz) , 136.69, 129.54, 129.43 (d, J=7.8 Hz), 127.82, 115.25 (d, J=21.2 Hz), 79.72, 73.11, 56 .76, 49.18, 34.67, 28.31, 20.97, 19.28, 18.12. 307

(Thin Film) 3370, 2980, 2936, 1712, 1503, 1453, 1366, 1164, 1053, 966, 851, 698 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₃ H ₂₈ F ₂ NO ₄ , 420.1981; found 420,1995 ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.33-7.24 (m, 5H), 7.22-7.14 (m, 1H), 6.86-6.73 (m, 2H), 5.84-5.72 (m, 1H), 4.90 (d, J=8.0 Hz, 1H), 4.40 (d, J=10.2 Hz, 1H), 4.18-4 .05 (m, 1H), 1.42 (s, 9H), 1.26 (d, J=6.1 Hz, 3H), 0.78 (d, J=7.2 Hz, 3H).
¹³ C NMR (126 MHz, CDCl ₃ ) δ 172.74, 162.98-161.09 (m), 160.06 (dd, J=169.5, 12.1 Hz), 154.93, 140, 15, 129.79, 128.61, 128.22, 127.00, 124.39 (d, J=18.6 Hz), 111.62 (d, J=19.5 Hz), 104.70- 103.41 (m), 79.71, 72.30, 49.40, 49.15, 34.67, 28.31, 18.97, 17.99. 308

(Thin Film) 3364, 2980, 2933, 1713, 1502, 1453, 1366, 1164, 1053, 966, 850 HRMS-ESI (m/z) ([M+Na] ⁺ ) calculated for C ₂₄ H ₂₉ F ₂ NO ₄ Na, 456.1957; found 456,1953 ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.25-7.20 (m, 1H), 7.18 (d, J=8.1 Hz, 2H), 7.07 (d, J=7, 6 Hz, 2H), 6.85-6.72 (m, 2H), 5.76 (dtd, J=9.5, 6.8, 5.5 Hz, 1H), 4.92 (d, J =7.8 Hz, 1H), 4.36 (d, J=10.0 Hz, 1H), 4.19-4.01 (m, 1H), 2.27 (s, 3H), 1.42 (s, 9H), 1.25 (d, J=6.2 Hz, 3H), 0.82 (d, J=7.2 Hz, 3H).
¹³ C NMR (126 MHz, CDCl ₃ ) δ 172.74, 161.98 (dd, J=167.8, 11.9 Hz), 160.01 (dd, J=167.8, 11.9 Hz) , 154.93, 137.05, 136.57, 129.90, 129.24, 128.11, 124.66 (d, J=11.5 Hz), 111.57 (d, J=20.4 Hz), 104.69-102.95 (m), 79.70, 72.38, 49.18, 48.94, 28.31, 20.97, 18.97, 18.07. 309

(Thin Film) 3364, 2981, 1711, 1604, 1502, 1454, 1380, 1366, 1224, 1161, 1053, 966, 851, HRMS-ESI (m/z) ([M+Na] ⁺ ) calculated for C ₂₃ H ₂₆ F ₃ NO ₄ Na, 460.1706; found 460,1712 ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.29-7.19 (m, 3H), 6.99-6.93 (m, 2H), 6.86-6.75 (m, 2H), 5.81-5.70 (m, 1H), 4.90 (d, J=7.9 Hz, 1H), 4.37 (d, J=10.1 Hz, 1H), 4.21-4 .06 (m, 1H), 1.42 (s, 9H), 1.26 (d, J=6.2 Hz, 3H), 0.85 (dd, J=7.8, 1.1 Hz, 3H).
¹³ C NMR (126 MHz, CDCl ₃ ) δ 172.71, 162.85, 162.71, 161.37, 161.28, 160.87, 160.75, 159.39, 159.30, 154.93 , 135.92, 129.76 (d, J=7.7 Hz), 115.44 (d, J=21.3 Hz), 111.71 (d, J=18.0 Hz), 104.71 -103.96 (m), 79.80, 72.20, 49.16, 48.78, 34.67, 28.30, 18.99, 18.09. 310

HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₆ H ₃₈ NO ₂ , 396.2897; found 396,2896 311

HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₄ H ₃₄ NO ₂ , 368.2584; found 368,2584 ¹H NMR (400 MHz, acetone-d₆)5 7.31-7.21 (m, 4H), 7.15 (ddd, J=10.9, 8.5, 2.5 Hz, 4H), 5.87 (dc, J=10.0 , 6.0 Hz, 1H), 4.05 (d, J=10.5 Hz, 1H), 3.85 (c, J=7.2 Hz, 1H), 3.31 (dt, J=3 .3, 1.7 Hz, 3H), 2.91-2.73 (m, 2H), 1.26 (d, J=6.1 Hz, 3H), 1.19 (t, J=6, 7 Hz, 12H), 0.81 (dd, J=7.3, 2.8 Hz, 3H). 312

HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₂ H ₃₀ NO ₂ , 340.2271; found 340,2273 313

HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₀ H ₂₄ F ₂ NO ₂ , 348.1770; found 348,1780 ¹H NMR (400 MHz, acetone-d₆) 5 7.34 (dd, J=8.7, 5.7 Hz, 1H), 7.26 (dd, J=8.7, 5.8 Hz, 1H), 7.02-6.80 ( m, 5H), 5.75 (dc, J=9.8, 6.1 Hz, 1H), 4.59 (d, J=9.8 Hz, 1H), 3.96 (c, J=7 .2 Hz, 1H), 3.72-3.60 (m, 2H), 2.40 (s, 3H), 2.37 (s, 3H), 1.34 (d, J=6.2 Hz , 3H), 1.03 (d, J=7.3 Hz, 3H).
¹⁹F NMR (376 MHz, acetone) 5-119.66, -120.05. 314

ESIMS m/z 320 ([M+H] ⁺ ) 315

ESIMS m/z 320 ([M+H] ⁺ ) 316

ESIMS m/z 380.5 ([M+H] ⁺ ) 317

ESIMS m/z 374.4 ([M+H] ⁺ ) 318

ESIMS m/z 298 ([M+H] ⁺ ) 319

ESIMS m/z 334 ([M+H] ⁺ ) 320

ESIMS m/z 420 ([M+H] ⁺ ) 321

ESIMS m/z 428 ([M+H] ⁺ ) 322

(Thin Film) 2851, 1740, 1494, 1451, 1253, 1231, 1204, 1117, 1080, 1046, 871, 746, 699 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₁₈ H ₂₂ NO ₂ , 284.1645; found 284,1644 323

ESIMS m/z 412.3 ([M+H] ⁺ ) 324

ESIMS m/z 408.4 ([M+H] ⁺ ) 325

ESIMS m/z 440.3 ([M+H] ⁺ ) 326

ESIMS m/z 400.4 ([M+H] ⁺ ) 327

ESIMS m/z 404 ([M+H] ⁺ ) 328

ESIMS m/z 372 ([M+H] ⁺ ) 329

ESIMS m/z 372 ([M+H] ⁺ ) 330

ESIMS m/z 380 ([M+H] ⁺ ) 331

ESIMS m/z 380 ([M+H] ⁺ ) 332

HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₀ H ₂₄ F ₂ NO ₄ , 380.1668; found 380,1649 ¹ H NMR (500 MHz, methanol-d ₄ ) δ 6.74 (dddd, J=17.6, 8.0, 3.7, 1.8 Hz, 4H), 6.58 (ddt, J=12 .2, 10.0, 2.3 Hz, 2H), 5.83 (dc, J=10.2, 6.1 Hz, 1H), 4.13 (d, J=10.3 Hz, 1H) , 3.93 (q, J=7.2 Hz, 1H), 3.78 (s, 3H), 3.77 (s, 3H), 1.28 (d, J=6.2 Hz, 3H) , 1.00 (d, J=7.3 Hz, 3H) (NH protons were not observed).
¹⁹ F NMR (471 MHz, methanol-d ₄ ) δ -112.85 (t, J=10.0 Hz), -113.22 (t, J=10.3 Hz). 333

HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₂ H ₃₀ NO ₆ , 404.2068; found 404,2038 ¹ H NMR (500 MHz, methanol-d ₄ ) δ 6.51 (dd, J=5.2, 2.3 Hz, 4H), 6.35 (dt, J=13.0, 2.2 Hz, 2H), 5.82 (dc, J=10.4, 6.1 Hz, 1H), 3.99 (d, J=10.4 Hz, 1H), 3.89 (c, J=7.2 Hz, 1H), 3.75 (s, 6H), 3.74 (s, 6H), 1.27 (d, J=6.2 Hz, 3H), 0.96 (d, J=7.3 Hz, 3H) (NH protons were not observed). 334

HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₂ H ₃₀ NO ₄ , 372.2169; found 372,2146 ¹ H NMR (500 MHz, methanol-d ₄ ) δ 6.75 (d, J=4.0 Hz, 2H), 6.69 (dt, J=6.6, 1.9 Hz, 2H), 6 .61 (s, 1H), 6.58 (d, J=2.3 Hz, 1H), 5.82 (dc, J=10.4, 6.1 Hz, 1H), 3.97 (d, J=10.5Hz, 1H), 3.85(k, J=7.3Hz, 1H), 3.75(s, 3H), 3.74(s, 3H), 2.29(s, 3H), 2.27 (s, 3H), 1.25 (d, J=6.2 Hz, 3H), 0.92 (d, J=7.2 Hz, 3H) (NH protons were not observed). 335

HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₂ H ₃₀ NO ₄ , 372.2169; found 372,2146 ¹ H NMR (500 MHz, methanol-d ₄ ) δ 6.75 (d, J=4.0 Hz, 2H), 6.69 (dt, J=6.6, 1.9 Hz, 2H), 6 .61 (s, 1H), 6.58 (d, J=2.3 Hz, 1H), 5.82 (dc, J=10.4, 6.1 Hz, 1H), 3.97 (d, J=10.5Hz, 1H), 3.85(k, J=7.3Hz, 1H), 3.75(s, 3H), 3.74(s, 3H), 2.29(s, 3H), 2.27 (s, 3H), 1.25 (d, J=6.2 Hz, 3H), 0.92 (d, J=7.2 Hz, 3H) (NH protons were not observed). 336

ESIMS m/z 372A ([M+H] ⁺ ) ¹ H NMR (500 MHz, methanol-d ₄ ) δ 7.03 (dd, J=11.9, 7.5 Hz, 2H), 6.92-6.80 (m, 4H), 5.88 ( dc, J=10.5, 6.1 Hz, 1H), 4.05 (d, J=10.4 Hz, 1H), 3.88 (c, J=7.2 Hz, 1H), 3, 80 (d, J=1.0 Hz, 6H), 2.12 (s, 3H), 2.11 (s, 3H), 1.26 (d, J=6.1 Hz, 3H), 0, 90 (d, J=7.2 Hz, 3H) (NH protons were not observed). 337

HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₀ H ₂₄ F ₂ NO ₄ , 380.1668; found 380,1667 ¹ H NMR (500 MHz, methanol-d ₄ ) δ 7.15-7.06 (m, 4H), 7.03 (q, J=8.5 Hz, 2H), 5.77 (dc, J= 10.1, 6.2 Hz, 1H), 4.06 (d, J=10.0 Hz, 1H), 3.93 (c, J=7.3 Hz, 1H), 3.83 (s, 3H), 3.82 (s, 3H), 1.25 (d, J=6.1 Hz, 3H), 1.00 (d, J=7.3 Hz, 3H) (NH protons were not observed).
¹⁹ F NMR (471 MHz, methanol-d ₄ ) δ -136.28 (dd, J=12.6, 8.5 Hz), -136.53 (dd, J=12.6, 8.9 Hz) . 338

ESIMS m/z 372A ([M+H] ⁺ ) ¹ H NMR (500 MHz, methanol-d ₄ )5 7.14-7.03 (m, 4H), 6.80 (dd, J=12.7, 8.4 Hz, 2H), 5.77 ( dc, J=10.3, 6.2 Hz, 1H), 3.92 (d, J=10.4 Hz, 1H), 3.86 (c, J=7.2 Hz, 1H), 3, 78 (s, 3H), 3.76 (s, 3H), 2.15 (s, 3H), 2.14 (s, 3H), 1.23 (d, J=6.1 Hz, 3H), 0.92 (d, J=7.3 Hz, 3H) (NH protons were not observed). 339

HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₂ H ₃₀ NO ₆ , 404.2068; found 404,2059 ¹ H NMR (500 MHz, methanol-d ₄ ) δ 7.03 (d, J=3.0 Hz, 1H), 6.90-6.80 (m, 3H), 6.75 (ddd, J= 8.9, 4.5, 3.1 Hz, 2H), 5.99 (dc, J=10.2, 6.2 Hz, 1H), 4.91 (d, J=10.2 Hz, 1H ), 3.89 (q, J=7.2 Hz, 1H), 3.81 (s, 3H), 3.73 (s, 3H), 3.73 (s, 3H), 3.70 (s , 3H), 1.24 (d, J=6.2 Hz, 3H), 0.97 (d, J=7.2 Hz, 3H) (NH protons were not observed). 340

(Thin Film) 2938, 1742, 1617, 1501, 1473, 1429, 1293, 1233, 1189, 1119, 1050, 950, 785 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₀ H ₂₂ F ₄ NO ₄ , 416.1479; found 416,1479 341

(Thin Film) 2866, 1742, 1500, 1454, 1378, 1226, 1113, 1048, 808, 792, 737 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₂ H ₃₀ NO ₂ , 340.2271; found 340,2269 342

(Thin Film) 2863, 1748, 1736, 1526, 1500, 1456, 1376, 1238, 1187, 1116, 1048, 810, 791, 751 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₂ H ₃₀ NO ₂ , 340.2271; found 340,2274 343

(Thin Film) 2878, 1751, 1738, 1587, 1526, 1494, 1459, 1240, 1226, 1188, 1130, 1048, 811, 754 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₀ H ₂₄ F ₂ NO ₂ , 348.1770; found 348,1771 344

(Thin Film) 2962, 1747, 1596, 1497, 1234, 1205, 1114, 1052, 1034, 829, 811, 713 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₀ H ₂₄ F ₂ NO ₄ , 380.1668; found 380,1665 345

(Thin Film) 2839, 1744, 1622, 1583, 1506, 1444, 1287, 1254, 1193, 1116, 1050, 1030, 872, 833 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₀ H ₂₄ F ₂ NO ₄ , 380.1668; found 380,1671 346

(Thin Film) 2941, 1742, 1615, 1588, 1457, 1417, 1326, 1241, 1171, 1116, 1032, 873, 859, 740 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₂ H ₂₄ F ₆ NO ₄ , 480.1604; found 480,1607 347

ESIMS m/z 408.2 ([M+H] ⁺ ) 348

ESIMS m/z 436.2 ([M+H] ⁺ ) 349

ESIMS m/z 404.1 ([M+H] ⁺ ) 350

ESIMS m/z 372A ([M+H] ⁺ ) 351

ESIMS m/z 372A ([M+H] ⁺ ) 352

ESIMS m/z 380 ([M+H] ⁺ ) 353

ESIMS m/z 372 ([M+H] ⁺ ) 354

ESIMS m/z 332 ([M+H] ⁺ ) 355

ESIMS m/z 316 ([M+H] ⁺ ) 356

ESIMS m/z 332 ([M+H] ⁺ ) 357

ESIMS m/z 316 ([M+H] ⁺ ) 358

ESIMS m/z 346 ([M+H] ⁺ ) 359

ESIMS m/z 330 ([M+H] ⁺ ) 360

ESIMS m/z 346 ([M+H] ⁺ ) 361

ESIMS m/z 350 ([M+H] ⁺ ) 362

ESIMS m/z 334 ([M+H] ⁺ ) 363

ESIMS m/z 350 ([M+H] ⁺ ) 364

ESIMS m/z 334 ([M+H] ⁺ ) 365

ESIMS m/z 312 ([M+H] ⁺ ) 366

ESIMS m/z 364.2 ([M+H] ⁺ ) 367

ESIMS m/z 368.2 ([M+H] ⁺ ) 368

ESIMS m/z 364.2 ([M+H] ⁺ ) 369

ESIMS m/z 352.2 ([M+H] ⁺ ) 370

ESFMS m/z 316 ([M+H] ⁺ ) 371

ESFMS m/z 334 ([M+H] ⁺ ) 372

ESIMS m/z 330 ([M+H] ⁺ ) 373

ESFMS m/z 348 ([M+H] ⁺ ) 374

ESIMS m/z 352 ([M+H] ⁺ ) 375

ESIMS m/z 316 ([M+H] ⁺ ) 376

ESIMS m/z 364 ([M+H] ⁺ ) 377

(Thin Film) 3408, 2920, 1740, 1512, 1495, 1452, 1232, 1198, 1114, 1048, 734, 699 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₁₉ H ₂₄ NO ₂ , 298.1802; found 298,1798 378

(Thin Film) 2877, 1749, 1599, 1515, 1493, 1452, 1228, 1193, 1139, 1119, 1055, 744, 699 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₁₉ H ₂₄ NO ₂ , 298.1802; found 298.1795 379

(Thin Film) 2879, 1747, 1602, 1508, 1454, 1227, 1197, 1116, 1053, 814, 733 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₁₉ H ₂₃ FNO ₂ , 316.1707; found 316,1703 380

(Thin Film) 2896, 1741, 1604, 1509, 1453, 1226, 1117, 1047, 732, 699 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₁₈ H ₂₁ FNO ₂ , 302.1551; found 302,1548 381

(Thin film) 2919, 1741, 1603, 1509, 1459, 1229, 1117, 1049, 813 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₁₉ H ₂₃ FNO ₂ , 316.1707; found 316,1705 382

(Thin Film) 3396, 2936, 1743, 1619, 1602, 1503, 1454, 1235, 1208, 1145, 1116, 966, 850, 699 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₁₈ H ₂₀ F ₂ NO ₂ , 320.1457; found 320,1451 383

(Thin Film) 3440, 2924, 1743, 1603, 1502, 1234, 1208, 1116, 1100, 1083, 966, 849 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₁₉ H ₂₂ F ₂ NO ₂ , 334.1613; found 334,1606 384

(Thin Film) 3384, 2935, 1743, 1603, 1503, 1228, 1117, 966, 850 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₁₈ H ₁₉ F ₃ NO ₂ , 338.1362; found 338,1356 385

(Thin Film) 3384, 2935, 1743, 1603, 1503, 1228, 1117, 966, 850 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₁₈ H ₁₉ F ₃ NO ₂ , 338.1362; found 338,1356 386

HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₅ H ₂₅ F ₂ N ₂ O ₅ , 471.1728; found 471,1726. ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.05 (d, J=0.6 Hz, 1H), 8.31 (d, J=8.0 Hz, 1H), 7.97 (d, J =5.2 Hz, 1H), 7.22 (dddd, J=11.7, 8.5, 5.3, 2.6 Hz, 4H), 7.02-6.89 (m, 4H), 6.86 (d, J=5.2 Hz, 1H), 5.72 (dc, J=9.7, 6.2 Hz, 1H), 4.60-4.46 (m, 1H), 4 .05 (d, J=9.8 Hz, 1H), 3.94 (s, 3H), 1.24 (d, J=6.2 Hz, 3H), 1.06 (d, J=7, 2 Hz, 3H).
¹³ C NMR (101 MHz, CDCl ₃ ) δ 171.56, 168.60, 162.98, 162.87, 160.54, 160.42, 155.41, 148.75, 140.43, 136.83 , 136.80, 136.73, 136.70, 130.36, 129.54, 129.46, 115.83, 115.62, 115.50, 115.29, 109.46, 73.32, 56 .14, 56.08, 47.87, 30.92, 19.12, 17.67. 387

HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₅ H ₂₅ F ₂ N ₂ O ₅ , 471.1723; found 471,1726. ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.08 (d, J=0.7 Hz, 1H), 8.20 (d, J=8.0 Hz, 1H), 7.99 (d, J =5.2 Hz, 1H), 7.24-7.13 (m, 4H), 7.03-6.93 (m, 2H), 6.93-6.84 (m, 3H), 5, 69 (dc, J=9.1, 6.2 Hz, 1H), 4.59-4.45 (m, 1H), 4.05 (d, J=9.0 Hz, 1H), 3.96 (s, 3H), 1.34 (d, J=7.2 Hz, 3H), 1.22 (d, J=6.2 Hz, 3H).
¹³ C NMR (101 MHz, CDCl ₃ ) δ 171.26, 168.55, 162.94, 162.84, 160.49, 160.40, 155.44, 148.78, 140.44, 136.82 136.79 136.46 136.43 130.35 129.74 129.67 129.65 129.57 115.76 115.55 115.46 115.24 109 .50, 99.99, 73.34, 56.11, 55.66, 47.80, 18.95, 17.74. 388

(Thin Film) 3371, 2981, 1735, 1649, 1495, 1261, 954, 800, 728 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₇ H ₂₉ F ₂ N ₂ O ₅ , 499.2039; found 499,2044 ¹ H NMR (500 MHz, CDCl ₃ ) δ 12.05 (s, 1H), 8.32 (d, J=8.0 Hz, 1H), 7.98 (d, J=5.2 Hz, 1H ), 7.24 (dd, J=8.7, 5.8 Hz, 1H), 7.14 (dd, J=8.6, 5.8 Hz, 1H), 6.92-6.72 ( m, 5H), 5.64 (dc, J=9.8, 6.2 Hz, 1H), 4.53 (p, J=7.3 Hz, 1H), 4.44 (d, J=9 .7 Hz, 1H), 3.94 (s, 3H), 2.38 (s, 3H), 2.31 (s, 3H), 1.31 (d, J=6.1 Hz, 3H), 1.10 (d, J=7.2 Hz, 3H).
¹⁹ F NMR (471 MHz, CDCl ₃ ) δ -116.46 (td, J=8.8, 5.7 Hz), -116.87 (td, J=9.0, 5.9 Hz). 389

(Thin Film) 3370, 2962, 1735, 1649, 1527, 1264, 1145, 801, 729 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₃ H ₄₃ N ₂ O ₅ , 547.3166; found 547.3163 ¹ H NMR (500 MHz, CDCl ₃ ) δ 12.12 (s, 1H), 8.38 (d, J=7.9 Hz, 1H), 7.98 (d, J=5.2 Hz, 1H ), 7.29 (d, J=8.3 Hz, 2H), 7.25 (s, 6H), 6.86 (d, J=5.2 Hz, 1H), 5.80 (dc, J =10.3, 6.2 Hz, 1H), 4.48 (n, J=7.3 Hz, 1H), 3.98 (d, J=10.3 Hz, 1H), 3.93 (s , 3H), 1.28-1.25 (m, 12H), 1.24 (s, 9H), 0.83 (d, J=7.2 Hz, 3H).
¹³ C NMR (126 MHz, CDCl ₃ ) δ 171.76, 168.50, 155.32, 149.63, 149.44, 148.70, 140.42, 138.71, 138.13, 130.51 , 127.66, 127.63, 125.64, 125.36, 109.37, 74.03, 57.25, 56.05, 47.78, 34.37, 34.32, 31.31, 31 .30, 19.33, 17.40. 390

(Thin Film) 3370, 2959, 1734, 1649, 1527, 1450, 1280, 1145, 1045, 801, 729 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₁ H ₃₉ N ₂ O ₅ , 519.2853; found 519,2848 ¹ H NMR (500 MHz, CDCl ₃ ) δ 12.12 (s, 1H), 7.98 (d, J=5.2 Hz, 1H), 7.23 (dd, J=8.3, 2, 6 Hz, 5H), 7.13 (d, J=7.9 Hz, 2H), 7.09 (d, J=7.9 Hz, 2H), 6.86 (d, J=5.2 Hz , 1H), 5.80 (dc, J=10.4, 6.1 Hz, 1H), 4.49 (n, J=7.3 Hz, 1H), 3.98 (d, J=10, 2 Hz, 1H), 3.93 (s, 3H), 2.82 (tp, J=13.9, 6.9 Hz, 2H), 1.25 (d, J=6.1 Hz, 3H) , 1.20 (d, J=6.9 Hz, 6H), 1.16 (d, J=6.9 Hz, 6H), 0.86 (d, J=7.2 Hz, 3H).
¹³ C NMR (126 MHz, CDCl ₃ ) δ 171.75, 168.50, 155.32, 148.70, 147.36, 147.20, 140.41, 139.09, 138.58, 130.51 , 127.91, 126.79, 126.50, 109.37, 73.97, 57.39, 56.05, 47.80, 33.64, 33.62, 23.98, 23.97, 23 .93, 19.31, 17.45. 391

(Thin Film) 3370, 2959, 1734, 1649, 1576, 1450, 1262, 1147, 1050, 800, 728 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₉ H ₃₅ N ₂ O ₅ , 491.2540; found 491,2540 ¹ H NMR (500 MHz, CDCl ₃ ) δ 12.12 (s, 1H), 8.36 (d, J=7.9 Hz, 1H), 7.98 (d, J=5.2 Hz, 1H ), 7.07-6.89 (m, 6H), 6.86 (d, J=5.3 Hz, 1H), 5.76 (dc, J=10.3, 6.1 Hz, 1H) , 4.52 (n, J=7.3 Hz, 1H), 3.94 (s, 3H), 3.91 (d, J=10.3 Hz, 1H), 2.17 (dd, J= 20.2, 12.3 Hz, 12H), 1.24 (d, J=6.1 Hz, 3H), 0.99 (d, J=7.2 Hz, 3H).
¹³ C NMR (126 MHz, CDCl ₃ ) δ 171.72, 168.48, 155.32, 148.69, 140.38, 139.15, 138.98, 136.84, 136.38, 135.01 , 134.59, 130.50, 129.93, 129.62, 129.33, 129.28, 125.27, 124.99, 109.35, 73.76, 57.12, 56.05, 47 .88, 19.88, 19.79, 19.30, 19.29, 19.24, 17.67. 392

(Thin film) 3358, 2936, 1749, 1659, 1508, 1223, 1131 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₅ H ₂₂ F ₅ N ₂ O ₅ , 525.1443; found 525,1451 ¹ H NMR (400 MHz, CDCl ₃ ) δ 11.51-11.26 (m, 1H), 8.72-8.46 (m, 1H), 8.10-7.95 (m, 1H), 7.24-7.13(m, 4H), 7.03-6.82(m, 5H), 5.88-5.70(m, 1H), 5.31-5.11(m, 1H ), 4.12-4.04 (m, 1H), 4.01-3.93 (m, 3H), 1.32-1.25 (m, 3H). 393

(Thin Film) 3371, 2939, 1734, 1649, 1599, 1500, 1277, 1150, 1034, 953 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₇ H ₂₉ F ₂ N ₂ O ₇ , 531.1937; found 531,1926 ¹ H NMR (300 MHz, CDCl ₃ ) δ 12.11 (d, J=0.7 Hz, 1H), 8.34 (d, J=8.0 Hz, 1H), 7.97 (d, J =5.3Hz, 1H), 7.35(dd, J=8.5, 6.7Hz, 1H), 7.25-7.08(m, 1H), 6.86(d, J= 5.2 Hz, 1H), 6.61-6.45 (m, 4H), 5.89 (dc, J=9.6, 6.1 Hz, 1H), 4.83 (d, J=9 .7 Hz, 1H), 4.71-4.44 (m, 1H), 3.94 (s, 3H), 3.83 (s, 3H), 3.73 (s, 3H), 1.23 (d, J=6.2 Hz, 3H), 1.09 (d, J=7.2 Hz, 3H). 394

HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₆ H ₂₉ N ₂ O ₅ , 448.2071; found 449,2081. ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.09 (s, 1H), 8.41 (d, J=7.9 Hz, 1H), 7.98 (d, J=5.2 Hz, 1H ), 7.32-7.12 (m, 10H), 6.86 (d, J=5.2 Hz, 1H), 5.87 (k, J=6.3 Hz, W), 4.59 (n, J=7.2 Hz, 1H), 3.94 (s, 3H), 1.75 (s, 3H), 1.20-1.14 (m, 6H).
¹³ C NMR (101 MHz, CDCl ₃ ) δ 171.61, 168.58, 155.36, 148.74, 146.44, 144.98, 140.40, 130.48, 128.16, 128.10 , 127.93, 127.35, 126.33, 126.16, 109.43, 76.21, 56.06, 50.40, 48.00, 23.98, 17.94, 15.94. 395

(Thin Film) 3370, 2981, 1734, 1648, 1575, 1527, 1494, 1480, 1450, 1279, 1262, 1242, 1144, 1047, 909, 729, 702 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₅ H ₂₇ N ₂ O ₅ , 435.1914; found 435,1924 Mixture of diastereomers 1:1. ¹ H NMR (500 MHz, CDCl ₃ ) δ 12.14 (s, 1H), 12.09 (s, 1H), 8.34 (d, J=8.0 Hz, 1H), 8.24 (d , J=7.9 Hz, 1H), 8.00 (d, J=5.2 Hz, 1H), 7.98 (d, J=5.2 Hz, 1H), 7.32-7.17 (m, 9H), 7.16-7.10 (m, 1H), 6.88 (d, J=5.2 Hz, 1H), 6.86 (d, J=5.2 Hz, 1H) , 5.88-5.75 (m, 1H), 4.56-4.44 (m, 1H), 4.07 (d, J=5.6 Hz, 1H), 4.05 (d, J =6.1 Hz, 1H), 3.95 (s, 3H), 3.94 (s, 1H), 1.29 (d, J=7.2 Hz, 3H), 1.26 (d, J =6.2 Hz, 3H), 1.24 (d, J=6.2 Hz, 3H), 0.97 (d, J=7.2 Hz, 3H). 396

(Thin Film) 3372, 2985, 2228, 1738, 1649, 1576, 1529, 1504, 1452 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₇ H ₂₅ N ₄ O ₅ , 485.1819; found 485,1824 ¹ H NMR (400 MHz, CDCl ₃ ) δ 11.96 (s, 1H), 8.24 (d, J=1.9 Hz, 1H), 7.98 (t, J=5.4 Hz, 1H ), 7.63-7.59 (m, 2H), 7.57-7.50 (m, 2H), 7.40-7.37 (m, 2H), 7.37-7.33 (m , 2H), 6.93-6.84 (m, 1H), 5.83-5.71 (m, 1H), 4.61-4.46 (m, 1H), 4.21 (d, J =9.3 Hz, 1H), 3.96 (s, 3H), 1.28 (d, J=6.1 Hz, 3H), 1.13 (d, J=1.2 Hz, 3H). 397

(Thin film) 2984, 1739, 1681, 1617, 1577, 1530, 1482 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₇ H ₂₅ F ₆ N ₂ O ₅ , 571.1662; found 571,1671 ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.01 (s, 1H), 8.31 (d, J=8.0 Hz, 1H), 7.98 (d, J=5.2 Hz, 1H ), 7.57 (d, J=8.1 Hz, 2H), 7.52 (d, J=8.3 Hz, 2H), 7.42 (d, J=8.3 Hz, 2H), 7.39 (d, J=8.3 Hz, 2H), 6.87 (d, J=5.3 Hz, 1H), 5.90-5.82 (m, 1H), 4.59-4 .48 (m, 1H), 4.22 (d, J=9.6 Hz, 1H), 3.94 (s, 3H), 1.29 (d, J=6.2 Hz, 3H), 1 .03 (d, J=7.2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -62.66, -62.69. 398

(Thin Film) 3364, 2981, 1713, 1650, 1607, 1529, 1481, 1418 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₁ H ₃₅ N ₂ O ₉ , 579.2337; found 579,2349 ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.03 (s, 1H), 8.33 (d, J=8.0 Hz, 1H), 8.00-7.95 (m, 3H), 7 .93 (d, J=8.4 Hz, 2H), 7.38 (d, J=8.4 Hz, 2H), 7.35 (d, J=8.3 Hz, 2H), 6.86 (d, J=5.2 Hz, 1H), 5.86 (dp, J=9.1, 7.1, 6.6 Hz, 1H), 4.60-4.50 (m, lH), 4.35 (cd, J=7.1, 2.8 Hz, 4H), 4.22 (d, J=9.7 Hz, 1H), 3.93 (s, 3H), 1.37 (t , J=7.2 Hz, 3H), 1.37 (t, J=7.1 Hz, 3H), 1.28 (d, J=6.2 Hz, 3H), 1.05 (d, J =7.2 Hz, 3H). 399

(Thin Film) 3364, 2939, 1734, 1649, 1488, 1449, 1243 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₇ H ₂₉ Cl ₂ N ₂ O ₇ , 563.1346; found 563,1354 ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.10 (s, 1H), 8.34 (d, J=7.9 Hz, 1H), 7.96 (d, J=5.2 Hz, 1H ), 7.32 (d, J=8.3 Hz, 1H), 7.09 (d, J=8.7 Hz, 1H), 6.86 (d, J=5.3 Hz, 1H), 6.85-6.80 (m, 3H), 6.74 (d, J=2.0 Hz, 1H), 5.88 (dc, J=9.6, 6.2 Hz, 1H), 4 .83 (d, J=9.7 Hz, 1H), 4.54 (n, J=7.2 Hz, 1H), 3.94 (s, 3H), 3.83 (s, 3H), 3 .74 (s, 3H), 1.23 (d, J=6.2 Hz, 3H), 1.11 (d, J=7.2 Hz, 3H). 400

(Thin Film) 3373, 2980, 1734, 1649, 1598, 1480, 1263, 1161, 1040 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₉ H ₃₃ F ₂ N ₂ O ₇ , 559.225; found 559,2258 ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.12 (s, 1H), 8.36 (d, J=7.9 Hz, 1H), 7.96 (d, J=5.2 Hz, 1H ), 7.32 (dd, J=8.5, 6.8 Hz, 1H), 7.15 (dd, J=9.0, 6.9 Hz, 1H), 6.85 (d, J= 5.2 Hz, 1H), 6.62-6.39 (m, 4H), 5.99-5.89 (m, 1H), 4.82 (d, J=10.1 Hz, 1H), 4.55 (p, J=7.2 Hz, 1H), 4.03-3.81 (m, 7H), 1.47 (t, J=7.0 Hz, 3H), 1.40 (t , J=7.0 Hz, 3H), 1.24 (d, J=6.1 Hz, 3H), 1.10 (d, J=7.2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -113.62, -114.03. 401

(Thin Film) 3367, 2980, 1735, 1650, 1576, 1528, 1243, 1147, 1041 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₉ H ₃₃ Cl ₂ N ₂ O ₇ , 591.1659; found 591,1662 ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.10 (s, 1H), 8.36 (d, J=7.9 Hz, 1H), 7.96 (d, J=5.2 Hz, 1H ), 7.29 (d, J=8.3 Hz, 1H), 7.11 (d, J=8.2 Hz, W), 6.85 (d, J=5.3 Hz, 1H), 6.80 (dd, J=8.2, 2.0 Hz, 2H), 6.77 (d, J=2.0 Hz, 1H), 6.70 (d, J=2.1 Hz, 1H ), 5.92 (dc, J=10.2, 6.2 Hz, 1H), 4.82 (d, J=10.0 Hz, W), 4.62-4.47 (m, 1H) , 4.03-3.81 (m, 7H), 1.47 (t, J=6.9 Hz, 3H), 1.39 (t, J=6.9 Hz, 3H), 1.24 ( d, J=6.1 Hz, 3H), 1.12 (d, J=7.2 Hz, 3H). 402

(Thin Film) 3374, 2976, 1733, 1649, 1527, 1450, 1261, 1142, 1044 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₁ H ₃₉ N ₂ O ₇ , 551.2752; found 551,2716 ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.17 (s, 1H), 8.40 (d, J=7.9 Hz, 1H), 7.96 (d, J=5.2 Hz, 1H ), 7.28 (d, J=7.8 Hz, 1H), 7.13 (d, J=7.6 Hz, W), 6.84 (d, J=5.3 Hz, 1H), 6.70-6.50 (m, 4H), 5.96 (dc, J=10.4, 6.1 Hz, 1H), 4.90 (d, J=10.2 Hz, 1H), 4 .53 (n, J=7.2 Hz, 1H), 4.05-3.80 (m, 7H), 2.26 (s, 3H), 2.22 (s, 3H), 1.47 ( t, J=7.0 Hz, 3H), 1.39 (t, J=6.9 Hz, 3H), 1.24 (d, J=6.1 Hz, 3H), 1.04 (d, J=7.2 Hz, 3H). 403

HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₇ H ₂₉ F ₂ N ₂ O ₇ , 531.1944; found 531,1937 ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.04 (d, J=0.7 Hz, 1H), 8.31 (d, J=7.9 Hz, 1H), 7.97 (d, J =5.2 Hz, 1H), 7.05-6.90 (m, 2H), 6.90-6.77 (m, 5H), 5.73 (dc, J=10.0, 6.1 Hz, 1H), 4.63-4.47(m, 1H), 3.99(d, J=9.9Hz, 1H), 3.94(s, 3H), 3.86(s, 3H ), 3.85 (s, 3H), 1.26 (d, J=6.1 Hz, 3H), 1.08 (d, J=7.2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -137.02, -137.51. 404

HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₉ H ₃₅ N ₂ O ₇ , 523.2432; found 523.2426 ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.11 (s, 1H), 8.35 (d, J=8.0 Hz, 1H), 7.97 (d, J=5.2 Hz, 1H ), 7.20 (d, J=8.6 Hz, 1H), 7.16-7.08 (m, 1H), 6.86 (d, J=5.3 Hz, 1H), 6.71 -6.63 (m, 3H), 6.59 (d, J=2.8 Hz, 1H), 5.65 (dc, J=9.9, 6.1 Hz, 1H), 4.61- 4.46 (m, 1H), 4.39 (d, J=10.0 Hz, 1H), 3.94 (s, 3H), 3.75 (s, 3H), 3.72 (s, 3H ), 2.37 (s, 3H), 2.30 (s, 3H), 1.30 (d, J=6.2 Hz, 3H), 1.09 (d, J=7.2 Hz, 3H ).
¹³ C NMR (101 MHz, CDCl ₃ ) δ 171.70, 168.56, 157.82, 157.67, 155.37, 148.74, 140.37, 137.93, 137.69, 131.88 , 131.34, 130.50, 128.88, 128.13, 116.26, 116.08, 111.28, 110.86, 109.41, 75.02, 56.04, 55.08, 47 .93, 46.22, 20.36, 20.30, 18.82, 17.78. 405

(Thin Film) 3368, 2937, 2837, 1732, 1650, 1609, 1578, 1529, 1504 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₉ H ₃₅ N ₂ O ₉ , 555.2337; found 555.2327 ¹ H NMR (300 MHz, CDCl ₃ ) δ 12.16 (s, 1H), 8.37 (d, J=8.0 Hz, 1H), 7.97 (d, J=5.2 Hz, 1H ), 7.32 (d, J=8.4 Hz, 1H), 7.11 (d, J=8.4 Hz, 1H), 6.85 (d, J=5.3 Hz, 1H), 6.42-6.34 (m, 3H), 6.32 (d, J=2.5 Hz, 1H), 5.88 (dc, J=9.8, 6.2 Hz, 1H), 4 .82 (d, J=9.9 Hz, 1H), 4.61-4.46 (m, 1H), 3.94 (s, 3H), 3.82 (s, 3H), 3.75 ( s, 3H), 3.74 (s, 3H), 3.73 (s, 3H), 1.23 (d, J=6.2 Hz, 3H), 1.07 (d, J=7.2 Hz, 3H). 406

(Thin film) 3373, 2936, 1734, 1650, 1611, 1577, 1529, 1505 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₉ H ₃₅ N ₂ O ₇ , 523.2439; found 523.2437 ¹ H NMR (300 MHz, CDCl ₃ ) δ 12.16 (d, J=0.6 Hz, 1H), 8.38 (d, J=8.0 Hz, 1H), 7.97 (d, J =5.2 Hz, 1H), 7.30 (d, J=7.8 Hz, lH), 7.10 (d, J=8.1 Hz, 1H), 6.85 (dd, J=5 .3, 0.6 Hz, 1H), 6.70-6.59 (m, 3H), 6.57-6.53 (m, 1H), 5.92 (dc, J=9.9, 6 .2 Hz, 1H), 4.90 (d, J=9.9 Hz, 1H), 4.60-4.43 (m, 1H), 3.94 (s, 3H), 3.83 (s , 3H), 3.72 (s, 3H), 2.27 (s, 3H), 2.24 (s, 3H), 1.23 (d, J=6.2 Hz, 3H), 1.03 (d, J=1.2 Hz, 3H). 407

(Thin Film) 3370, 2937, 2936, 1734, 1650, 1576, 1528, 1501 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₉ H ₃₅ N ₂ O ₇ , 523.2439; found 523.2429 ¹ H NMR (300 MHz, CDCl ₃ ) δ 12.16 (d, J=0.6 Hz, 1H), 8.38 (d, J=7.9 Hz, 1H), 7.97 (d, J =5.2 Hz, 1H), 7.20 (d, J=2.2 Hz, 1H), 7.05 (d, J=2.2 Hz, 1H), 6.98-6.84 (m , 2H), 6.85 (dd, J=5.4, 0.6 Hz, 1H), 6.74 (d, J=8.3 Hz, 1H), 6.64 (d, J=8, 3 Hz, 1H), 5.88 (dc, J=10.2, 6.1 Hz, 1H), 4.96 (d, J=10.3 Hz, W), 4.60-4.45 ( m, 1H), 3.94 (s, 3H), 3.82 (s, 3H), 3.72 (s, 3H), 2.24 (s, 3H), 2.21 (s, 3H), 1.24 (d, J=6.1 Hz, 3H), 1.02 (d, J=7.2 Hz, 3H). 408

(Thin Film) 3368, 2940, 2839, 1736, 1650, 1577, 1528, 1478, 1453, 1434 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₇ H ₂₉ F ₂ N ₂ O ₇ , 531.1937; found 531,1942 ¹ H NMR (300 MHz, CDCl ₃ ) for both diastereomers from a 1:1 mixture d 12.14 (d, J=0.7 Hz, 1H), 12.07 (d, J=0.6 Hz, 1H) , 8.32 (d, J=8.6 Hz, 1H), 8.29 (d, J=8.4 Hz, W), 7.98 (d, J=5.3 Hz, W), 7 .97 (d, J=5.2 Hz, 1H), 7.20-7.11 (m, 2H), 7.01-6.82 (m, 12H), 5.82-5.63 (m , 2H), 5.04 (d, J=10.1 Hz, 1H), 5.03 (d, J=9.3 Hz, 1H), 4.63-4.42 (m, 2H), 3 .96 (s, 3H), 3.95 (s, 3H), 3.93 (d, J=2.1 Hz, 3H), 3.90 (d, J=2.1 Hz, 3H), 3 .78 (d, J=1.8 Hz, 3H), 3.78 (d, J=1.8 Hz, 3H), 1.37 (d, J=7.2 Hz, 3H), 1.27 (d, J=6.2 Hz, 3H), 1.26 (d, J=6.2 Hz, 3H), 1.13 (d, J=7.2 Hz, 3H). 409

(Thin film) 3368, 2940, 2839, 1736, 1650, 1528, 1495, 1482 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₇ H ₂₉ F ₂ N ₂ O ₇ , 531.1937; found 531,1937 ¹ H NMR (300 MHz, CDCl ₃ ) for the main isomer of a 2:1 mixture of diastereomers d 12.09 (d, J=0.6 Hz, 1H), 8.37 (d, J=8.0 Hz, 1H) , 7.98 (d, J=5.2 Hz, 1H), 7.16 (dd, J=9.6, 2.9 Hz, 1H), 6.96 (dd, J=9.3, 3 .2 Hz, 1H), 6.90-6.75 (m, 4H), 6.72 (d, J=4.7 Hz, 1H), 5.98-5.79 (m, 1H), 4 .91-4.83(m, 1H), 4.62-4.46(m, 1H), 3.94(s, 3H), 3.83(s, 3H), 3.73(s, 3H ), 1.25 (d, J=6.2 Hz, 3H), 1.11 (d, J=7.2 Hz, 3H). 410

HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₉ H ₃₅ N ₂ O ₉ , 555.2337; found 555,2317 ¹ H NMR (300 MHz, CDCl ₃ ) for 1:1 mixture of diastereomers δ 12.20 (s, 1H), 12.11 (s, 1H), 8.37 (d, J=7.8 Hz, 2H) , 7.97 (t, J=5.2 Hz, 2H), 7.09-6.81 (m, 10H), 6.78-6.68 (m, 4H), 5.79-5.59 (m, 2H), 5.11 (dd, J=9.8, 6.2 Hz, 2H), 4.52 (dp, J=10.0, 7.1 Hz, 2H), 3.95 ( s, 3H), 3.94 (s, 3H), 3.89 (s, 3H), 3.86 (s, 3H), 3.84 (s, 3H), 3.83 (s, 3H), 3.81 (s, 3H), 3.79 (s, 3H), 3.73 (s, 3H), 3.70 (s, 3H), 1.35 (d, J=7.2 Hz, 3H ), 1.27 (d, J=4.7 Hz, 3H), 1.25 (d, J=4.7 Hz, 3H), 1.08 (d, J=7.2 Hz, 3H
¹³ C NMR (126 MHz, CDCl ₃ ) for 1:1 mixture of diastereomers δ 171.68, 171.35, 168.48, 168.46, 155.31, 155.29, 152.81, 152.79, 152 .74, 152.72, 148.71, 148.67, 147.33, 147.31, 147.15, 147.12, 140.36, 134.98, 134.79, 134.67, 134.47 130.57 130.50 123.69 123.65 123.62 121.03 120.94 120.41 120.24 110.79 110.57 110.55 109 .35, 109.33, 73.98, 60.39, 60.37, 60.27, 56.07, 56.05, 55.65, 55.57, 55.55, 47.92, 47.90 , 41.96, 41.92, 18.80, 18.72, 18.04, 17.74. 411

HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₉ H ₃₅ N ₂ O ₇ , 523.2439; found 523,2409 ¹ H NMR (300 MHz, CDCl ₃ ) for 1:1 mixture of diastereomers δ 12.20 (d, J=0.5 Hz, 1H), 12.11 (d, J=0.5 Hz, 1H), 8 .36 (d, J=7.8 Hz, 2H), 7.98 (dd, J=5.9, 5.2 Hz, 2H), 7.32 (ddd, J=12.0, 7.2 , 2.1 Hz, 2H), 7.17-7.09 (m, 2H), 7.09-6.80 (m, 10H), 5.76-5.57 (m, 2H), 5, 08 (t, J=9.6 Hz, 2H), 4.59-4.41 (m, 2H), 3.96 (s, 3H), 3.94 (s, 3H), 3.83 (s , 3H), 3.79 (s, 3H), 3.69 (s, 3H), 3.68 (s, 3H), 2.36-2.19 (m, 12H), 1.33-1, 23 (m, 9H), 1.02 (d, J=7.2 Hz, 3H).
¹³ C NMR (126 MHz, CDCl ₃ ) for 1:1 mixture of diastereomers δ 171.66, 171.15, 168.48, 168.46, 156.89, 156.80, 156.76, 155.32, 148 .74, 148.69, 140.38, 140.33, 133.98, 133.84, 133.74, 133.69, 131.21, 131.19, 131.02, 130.98, 130.56 130.47 130.09 130.04 129.77 129.74 126.86 126.71 126.59 126.34 123.84 123.80 123.73 109 .36, 74.58, 74.50, 60.29, 60.22, 60.19, 56.08, 56.07, 47.89, 47.85, 41.76, 41.70, 19.02 , 18.93, 18.03, 17.65, 16.69, 16.66, 16.48, 16.45. 412

¹ H NMR (400 MHz, CDCl ₃ ) for 1:1 mixture of diastereomers δ 12.18 (s, 1H), 12.11 (s, 1H), 8.36 (d, J=7.9 Hz, 1H) , 8.28 (d, J=7.7 Hz, 1H), 8.06-7.91 (m, 2H), 7.11-7.00 (m, 4H), 6.95 (t, J =8.6 Hz, 2H), 6.89-6.82 (m, 4H), 6.70 (d, J=8.2 Hz, 2H), 6.65 (dd, J=8.0, 4.5 Hz, 2H), 5.70 (ddc, J=12.3, 6.1, 3.3, 2.6 Hz, 2H), 4.62 (dd, J=12.2, 9, 9 Hz, 2H), 4.49 (dp, J=22.0, 7.2 Hz, 2H), 3.94 (s, 3H), 3.93 (s, 3H), 3.79 (s, 3H), 3.79 (s, 3H), 3.75 (s, 3H), 3.74 (s, 3H), 2.29 (s, 3H), 2.26 (s, 3H), 2, 19 (s, 3H), 2.18 (s, 3H), 1.35-1.25 (m, 9H), 1.05 (d, J=7.2 Hz, 3H).
¹³ C NMR (101 MHz, CDCl ₃ ) for 1:1 mixture of diastereomers δ 171.69, 171.27, 168.52, 157.74, 157.55, 155.32, 148.73, 140.69, 140 .38, 140.12, 139.96, 130.52, 126.17, 126.11, 125.90, 125.55, 125.38, 120.47, 120.38, 119.87, 119.66 , 109.38, 108.32, 74.97, 74.87, 56.03, 55.46, 55.43, 47.92, 47.89, 47.53, 18.74, 18.72, 17 .98, 17.69, 11.84, 11.74, 11.42. 413

(Thin Film) 3374, 2941, 1737, 1650, 1529, 1501, 1476, 1453, 1431, 1281, 1263, 1243, 1058, 952, 801 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₇ H ₂₇ F ₄ N ₂ O ₇ , 567.1749; found 567,1750 ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.03 (s, 1H), 8.28 (d, J=8.0 Hz, 1H), 7.96 (d, J=5.3 Hz, 1H ), 7.05 (ddd, J=8.4, 5.6, 2.2 Hz, 1H), 6.89-6.72 (m, 4H), 5.67 (dc, J=9.6 , 6.2 Hz, 1H), 4.86 (d, J=9.6 Hz, 1H), 4.56 (dt, J=8.1, 7.0 Hz, 1H), 3.97 (d , J=2.4Hz, 3H), 3.95(s, 3H), 3.83(d, J=2.1Hz, 3H), 1.25(d, J=6.2Hz, 3H ), 1.20 (d, J=7.2 Hz, 3H).
¹³ C NMR (126 MHz, CDCl ₃ ) δ 171.48, 168.61, 155.43, 148.73, 147.12 (d, J=7.3 Hz), 146.96 (d, J=7 .6 Hz), 145.26 (d, J=13.9 Hz), 143.28 (d, J=13.8 Hz), 140.44, 130.25, 129.70, 129.47, 123 .09 (dd, J=8.2, 3.8 Hz), 122.45-122.20 (m), 110.82 (d, J=17.3 Hz), 110.57, 109.47, 72.53, 61.22 (d, J=4.1 Hz), 61.16 (d, J=3.6 Hz), 56.11, 47.96, 42.46, 18.74, 17, 75. 414

(Thin Film) 3369, 2925, 1735, 1650, 1576, 1528, 1501, 1481, 1451, 1331, 1280, 1263, 1212, 1145, 1045, 801, 733 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₉ H ₃₅ N ₂ O ₅ , 491.2540; found 491,2536 ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.11 (s, 1H), 8.35 (d, J=8.0 Hz, 1H), 7.98 (d, J=5.2 Hz, 1H ), 7.11-7.00 (m, 3H), 6.94-6.84 (m, 4H), 5.73-5.64 (m, 1H), 4.55-4.44 (m , 2H), 3.94 (s, 3H), 2.36 (s, 3H), 2.28 (s, 3H), 2.26 (s, 6H), 1.30 (d, J=6, 1 Hz, 3H), 1.03 (d, J=7.2 Hz, 3H).
¹³ C NMR (126 MHz, CDCl ₃ ) δ 171.84, 168.52, 155.34, 148.73, 140.40, 139.09, 138.45, 135.47, 135.11, 133.53 133.33, 130.60, 130.49, 130.27, 128.60, 127.81, 127.27, 126.95, 109.39, 75.10, 56.07, 47.89, 47 .34, 21.29, 21.22, 19.79, 19.75, 18.78, 17.66. 415

(Thin Film) 3369, 2937, 1734, 1649, 1576, 1527, 1500, 1480, 1450, 1329, 1280, 1262, 1242, 1139, 1043, 908, 799, 728 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₉ H ₃₅ N ₂ O ₅ , 491.2540; found 491,2536 ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.11 (s, 1H), 8.35 (d, J=8.0 Hz, 1H), 7.97 (d, J=5.2 Hz, 1H ), 7.18 (d, J=7.9 Hz, 1H), 7.12 (d, J=7.7 Hz, 1H), 6.98-6.89 (m, 3H), 6.87 -6.81 (m, 2H), 5.69 (dc, J=10.0, 6.2 Hz, 1H), 4.58-4.48 (m, 1H), 4.45 (d, J =10.0 Hz, 1H), 3.94 (s, 3H), 2.35 (s, 3H), 2.29 (s, 3H), 2.25 (s, 3H), 2.21 (s , 3H), 1.30 (d, J=6.2 Hz, 3H), 1.05 (d, J=7.2 Hz, 3H).
¹³ C NMR (126 MHz, CDCl ₃ ) δ 171.71, 168.51, 155.32, 148.69, 140.38, 136.43, 136.33, 136.15, 135.95, 135.90 , 135.58, 131.50, 131.15, 130.49, 127.77, 127.05, 126.85, 126.58, 109.37, 75.04, 56.06, 47.89, 46 .81, 20.84, 20.80, 20.12, 20.07, 18.85, 17.71. 416

(Thin Film) 3369, 2938, 1736, 1649, 1576, 1528, 1494, 1480, 1452, 1326, 1279, 1263, 1240, 1184, 1145, 1044, 910, 803, 728 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₇ H ₂₉ F ₂ N ₂ O ₅ , 499.2039; found 499,2035 ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.05 (s, 1H), 8.36 (d, J=8.0 Hz, 1H), 7.98 (d, J=5.2 Hz, 1H ), 7.12 (dd, J=8.4, 6.0 Hz, 1H), 7.06-7.00 (m, 2H), 6.93-6.77 (m, 4H), 5, 60 (dc, J=9.6, 6.2 Hz, 1H), 4.61-4.50 (m, 1H), 4.48 (d, J=9.6 Hz, 1H), 3.94 (s, 3H), 2.35 (s, 3H), 2.28 (s, 3H), 1.34 (d, J=6.2 Hz, 3H), 1.10 (d, J=7, 2 Hz, 3H).
¹³ C NMR (126 MHz, CDCl ₃ ) δ 171.60, 168.60, 161.36 (d, J=244.0 Hz), 155.35, 148.72, 140.57 (d, J=6 .5 Hz), 140.48, 139.99 (d, J=6.6 Hz), 132.34 (d, J=3.2 Hz), 132.07 (d, J=7.8 Hz) , 132.00 (d, J=3.3 Hz), 131.72 (d, J=7.9 Hz), 130.39, 114.85 (d, J=22.3 Hz), 114.32 (d, J=22.3 Hz), 113.72 (d, J=20.7 Hz), 113.42 (d, J=20.5 Hz), 109.44, 74.21, 56.08 , 47.79, 47.70, 19.41, 19.36, 18.76, 17.68. 417

(Thin Film) 3367, 2940, 1738, 1650, 1530, 1498, 1482, 1453, 1281, 1264, 1242, 1210, 1149, 1037, 802, 730 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₇ H ₂₉ F ₂ N ₂ O ₇ , 531.1937; found 531,1931 ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.07 (s, 1H), 8.34 (d, J=8.0 Hz, 1H), 7.98 (d, J=5.2 Hz, 1H ), 7.01-6.90 (m, 2H), 6.88-6.80 (m, 3H), 6.71 (ddd, J=8.9, 3.9, 3.1 Hz, 1H ), 6.64 (ddd, J=8.9, 3.9, 3.1 Hz, 1H), 5.85 (dc, J=12.2, 6.1 Hz, 1H), 4.70 ( d, J=10.4 Hz, 1H), 4.61-4.52 (m, 1H), 3.94 (s, 3H), 3.74 (s, 6H), 1.31 (d, J =6.1 Hz, 3H), 1.11 (d, J=7.2 Hz, 3H).
¹³ C NMR (126 MHz, CDCl ₃ ) δ 171.53, 168.53, 155.99 (d, J=24.2 Hz), 155.76-155.59 (m), 155.32, 154, 09 (d, J=24.6 Hz), 148.70, 140.40, 130.42, 127.85 (d, J=15.9 Hz), 127.56 (d, J=16.3 Hz) ), 116.26 (d, J=24.9 Hz), 115.93 (d, J=24.8 Hz), 115.16, 114.19, 113.04 (d, J=8.2 Hz ), 109.39, 72.25, 56.07, 55.69, 47.85, 43.42, 18.94, 17.72. 418

(Thin Film) 3369, 2938, 1737, 1650, 1623, 1577, 1529, 1507, 1481, 1443, 1320, 1282, 1264, 1242, 1195, 1154, 1031, 951, 849, 83 4, 800, 731 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₇ H ₂₉ F ₂ N ₂ O ₇ , 531.1937; found 531,1933 ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.09 (s, 1H), 8.34 (d, J=8.0 Hz, 1H), 7.97 (d, J=5.2 Hz, 1H ), 7.27 (t, J=8.6 Hz, 1H), 7.16 (t, J=8.5 Hz, 1H), 6.86 (d, J=5.2 Hz, 1H), 6.64-6.54 (m, 3H), 6.47 (dd, J=12.1, 2.6 Hz, 1H), 5.79 (dc, J=12.0, 6.1 Hz, 1H), 4.66-4.52 (m, 2H), 3.94 (s, 3H), 3.75 (s, 3H), 3.72 (s, 3H), 1.28 (d, J =6.1 Hz, 3H), 1.14 (d, J=7.2 Hz, 3H).
¹³ C NMR (126 MHz, CDCl ₃ ) δ 171.55, 168.55, 161.19 (d, J=245.6 Hz), 161.00 (d, J=245.8 Hz), 159.75 (d, J=11.3 Hz), 159.47 (d, J=11.3 Hz), 155.35, 148.69, 140.39, 130.42, 129.87 (d, J=6 .2 Hz), 129.23 (d, J=5.9 Hz), 119.53 (d, J=14.6 Hz), 119.33 (d, J=15.0 Hz), 110.16 (d, J=3.0 Hz), 109.66 (d, J=3.0 Hz), 109.38, 101.82 (d, J=26.7 Hz), 101.59 (d, J =26.6 Hz), 72.49, 56.05, 55.48 (d, J=6.8 Hz), 47.90, 41.70, 18.91, 17.79. 419

(Thin Film) 3370, 2941, 1737, 1651, 1616, 1577, 1529, 1454, 1417, 1326, 1241, 1119, 1080, 1032, 905, 860, 801, 738 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₉ H ₂₉ F ₆ N ₂ O ₇ , 631.1873; found 631,1876 ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.06 (s, 1H), 8.34 (d, J=8.0 Hz, 1H), 7.97 (d, J=5.2 Hz, 1H ), 7.54 (d, J=7.8 Hz, 1H), 7.30 (d, J=8.0 Hz, 1H), 7.12 (dd, J=7.9, 1.6 Hz , 2H), 7.04 (d, J=1.8 Hz, 1H), 6.98 (d, J=1.7 Hz, 1H), 6.86 (d, J=5.2 Hz, 1H ), 5.99 (dc, J=9.5, 6.2 Hz, 1H), 5.00 (d, J=9.4 Hz, 1H), 4.59-4.48 (m, 1H) , 3.94 (s, 3H), 3.89 (s, 3H), 3.81 (s, 3H), 1.26 (d, J=6.2 Hz, 3H), 1.05 (d, J=7.2 Hz, 3H).
¹³ C NMR (126 MHz, CDCl ₃ ) δ 171.62, 168.58, 157.53, 155.38, 148.73, 140.44, 132.32 (d, J=8.6 Hz), 130 .37, 130.18, 130.04, 129.47, 125.02, 122.83, 117.30, 116.98, 109.43, 107.83-106.97 (m), 72.18, 56.07, 55.75, 55.69, 47.82, 18.89, 17.66. 420

(Thin Film) 3369, 2940, 1737, 1592, 1453, 1135, 1057, 849, 730 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₇ H ₂₉ F ₂ N ₂ O ₇ , 531.1937; found 531,1924 ¹ H NMR (500 MHz, CDCl ₃ ) δ 12.04 (d, J=0.6 Hz, 1H), 8.34 (d, J=8.0 Hz, 1H), 7.98 (d, J =5.2Hz, 1H), 6.86(d, J=5.2Hz, 1H), 6.65-6.52(m, 4H), 6.45(ddt, J=24.3, 10.5, 2.2 Hz, 2H), 5.69 (dc, J=10.1, 6.1 Hz, 1H), 4.61-4.50 (m, 1H), 3.97-3 .91 (m, 4H), 3.77 (s, 3H), 3.75 (s, 3H), 1.29-1.24 (m, 3H), 1.11 (d, J=7.2 Hz, 3H).
¹⁹ F NMR (471 MHz, CDCl ₃ ) δ -110.48 - -110.65 (m), -111.08 (t, J=10.0 Hz). 421

(Thin Film) 3371, 2938, 1735, 1593, 1454, 1204, 1150, 1063, 730 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₉ H ₃₅ N ₂ O ₉ , 555.2337; found 555,2329 ¹ H NMR (500 MHz, CDCl ₃ ) δ 12.10 (s, 1H), 8.35 (d, J=8.0 Hz, 1H), 7.98 (d, J=5.2 Hz, 1H ), 6.86 (d, J=5.2 Hz, 1H), 6.46-6.43 (m, 4H), 6.27 (dt, J=26.6, 2.2 Hz, 2H) , 5.75 (dc, J=10.3, 6.1 Hz, 1H), 4.58-4.47 (m, 1H), 3.94 (s, 3H), 3.89 (d, J =10.5 Hz, 1H), 3.76 (s, 6H), 3.74 (s, 6H), 1.30-1.23 (m, 3H), 1.05 (d, J=7, 2 Hz, 3H).
¹³ C NMR (126 MHz, CDCl ₃ ) δ 171.70, 168.53, 160.93, 160.75, 155.32, 148.71, 143.38, 143.10, 140.39, 130.45 , 109.36, 106.42, 106.08, 98.42, 98.35, 73.11, 58.22, 56.06, 55.30, 55.26, 47.87, 19.21, 17 .70. 422

(Thin Film) 3372, 2937, 1735, 1594, 1528, 1452, 1151, 1065, 730 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₉ H ₃₅ N ₂ O ₇ , 523.2439; found 523.2434 ¹ H NMR (500 MHz, CDCl ₃ ) δ 12.11 (s, 1H), 8.36 (d, J=8.0 Hz, 1H), 7.98 (d, J=5.2 Hz, 1H ), 6.86 (d, J=5.2 Hz, 1H), 6.69 (dd, J=3.8, 1.8 Hz, 2H), 6.64 (t, J=1.9 Hz , 2H), 6.55 (t, J=2.0 Hz, 1H), 6.49 (t, J=1.9 Hz, 1H), 5.75 (dc, J=10.5, 6, 2 Hz, 1H), 4.58-4.48 (m, 1H), 3.94 (s, 3H), 3.89 (d, J=10.5 Hz, 1H), 3.76 (s, 3H), 3.73 (s, 3H), 2.29 (s, 3H), 2.25 (s, 3H), 1.25 (d, J=6.2 Hz, 3H), 1.00 ( e, J=7.1 Hz, 3H).
¹³ C NMR (126 MHz, CDCl ₃ ) δ 171.74, 168.51, 159.74, 159.61, 155.32, 148.70, 142.68, 142.37, 140.40, 139.79 , 139.36, 130.47, 121.27, 121.12, 112.62, 112.61, 111.34, 110.82, 109.36, 73.43, 57.89, 56.06, 55 .15, 55.11, 47.86, 21.69, 21.61, 19.25, 17.66. 423

(Thin Film) 3370, 2937, 1734, 1649, 1528, 1452, 1260, 1137, 1039, 729 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₉ H ₃₅ N ₂ O ₇ , 523.2439; found 523.2434 ¹ H NMR (500 MHz, CDCl ₃ ) δ 12.10 (s, 1H), 8.33 (d, J=8.0 Hz, 1H), 7.97 (d, J=5.2 Hz, 1H ), 7.02 (dd, J=7.5, 0.9 Hz, 1H), 6.97 (dd, J=7.6, 0.8 Hz, 1H), 6.86 (d, J= 5.2 Hz, 1H), 6.80 (dt, J=7.5, 2.1 Hz, 2H), 6.74 (d, J=1.6 Hz, 1H), 6.71 (d, J=1.6 Hz, 1H), 5.80 (dc, J=10.3, 6.1 Hz, 1H), 4.58-4.47 (m, 1H), 3.96 (d, J =10.3 Hz, 1H), 3.94 (s, 3H), 3.80 (s, 3H), 3.78 (s, 3H), 2.14 (s, 3H), 2.11 (s , 3H), 1.27 (d, J=6.1 Hz, 3H), 1.00 (d, J=7.2 Hz, 3H). 424

(Thin Film) 3370, 2938, 1736, 1515, 1442, 1275, 1216, 731 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₇ H ₂₉ F ₂ N ₂ O ₇ , 531.1937; found 531,1935 ¹ H NMR (500 MHz, CDCl ₃ ) δ 12.05 (s, 1H), 8.33 (d, J=8.0 Hz, 1H), 7.98 (d, J=5.2 Hz, 1H ), 7.01-6.91 (m, 4H), 6.91-6.79 (m, 3H), 5.65 (dc, J=9.6, 6.2 Hz, 1H), 4, 61-4.51 (m, 1H), 3.94 (s, 3H), 3.92 (d, J=9.7 Hz, 1H), 3.85 (s, 3H), 3.83 (s , 3H), 1.24 (d, J=6.1 Hz, 3H), 1.13 (d, J=7.2 Hz, 3H).
¹⁹ F NMR (471 MHz, CDCl ₃ ) δ -134.12 (dd, J=12.1, 8.5 Hz), -134.58 (dd, J=12.1, 8.7 Hz). 425

(Thin Film) 3370, 2941, 1734, 1649, 1503, 1243, 1135, 1033, 801, 729 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₉ H ₃₅ N ₂ O ₇ , 523.2439; found 523.2428 ¹ H NMR (500 MHz, CDCl ₃ ) δ 12.13 (d, J=0.6 Hz, 1H), 8.36 (d, J=8.1 Hz, 1H), 7.98 (d, J =5.1 Hz, 1H), 7.06 (ddd, J=9.0, 7.1, 2.4 Hz, 2H), 7.01 (d, J=2.0 Hz, 2H), 6 .86 (d, J=5.2 Hz, 1H), 6.72 (d, J=8.4 Hz, 1H), 6.68 (d, J=8.4 Hz, 1H), 5.71 (dc, J=10.1, 6.1 Hz, 1H), 4.58-4.48 (m, 1H), 3.94 (s, 3H), 3.88 (d, J=10.1 Hz, 1H), 3.77 (s, 3H), 3.74 (s, 3H), 2.16 (s, 3H), 2.12 (s, 3H), 1.24 (d, J=6 .2 Hz, 3H), 1.03 (d, J=7.1 Hz, 3H). 426

(Thin Film) 3372, 2940, 1735, 1650, 1498, 1223, 1047, 804, 730 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₉ H ₃₅ N ₂ O ₉ , 555.2337; found 555,2304 ¹ H NMR (500 MHz, CDCl ₃ ) δ 12.14 (s, 1H), 8.38 (d, J=8.0 Hz, 1H), 7.97 (d, J=5.2 Hz, 1H ), 7.05 (d, J=3.0 Hz, 1H), 6.88 (d, J=3.1 Hz, 1H), 6.85 (d, J=5.2 Hz, 1H), 6.77 (d, J=8.9 Hz, 1H), 6.72-6.55 (m, 3H), 5.94 (dc, J=10.1, 6.1 Hz, 1H), 4 .93 (d, J=10.1 Hz, 1H), 4.60-4.49 (m, 1H), 3.94 (s, 3H), 3.82 (s, 3H), 3.74 ( s, 3H), 3.71 (s, 6H), 1.28-1.22 (m, 3H), 1.04 (d, J=7.2 Hz, 3H).
¹³ C NMR (126 MHz, CDCl ₃ ) δ 171.72, 168.47, 155.28, 153.41, 153.37, 151.78, 151.70, 148.67, 140.35, 130.55 , 130.51, 116.43, 115.36, 112.05, 112.00, 111.68, 111.46, 109.31, 73.26, 56.27, 56.05, 55.62, 55 .57, 47.90, 18.87, 17.81. 427

(Thin Film) 3370, 2939, 1736, 1529, 1452, 1243, 1143, 1043, 801, 730 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₉ H ₃₅ N ₂ O ₇ , 523.2439; found 523.2420 ¹ H NMR (500 MHz, CDCl ₃ ) δ 12.10 (s, 1H), 8.36 (d, J=8.0 Hz, 1H), 7.97 (d, J=5.2 Hz, 1H ), 7.06 (d, J=8.4 Hz, 1H), 6.95 (d, J=8.4 Hz, 1H), 6.90 (d, J=2.7 Hz, 1H), 6.86 (d, J=5.2 Hz, 1H), 6.82 (d, J=2.7 Hz, 1H), 6.66 (dd, J=8.4, 2.7 Hz, 1H ), 6.60 (dd, J=8.3, 2.7 Hz, 1H), 5.67 (dc, J=10.0, 6.2 Hz, 1H), 4.58-4.49 ( m, 1H), 4.46 (d, J=10.1 Hz, 1H), 3.94 (s, 3H), 3.74 (s, 3H), 3.73 (s, 3H), 2, 34 (s, 3H), 2.26 (s, 3H), 1.32 (d, J=6.2 Hz, 3H), 1.05 (d, J=7.2 Hz, 3H). 428

(Thin Film) 3368, 2933, 1736, 1648, 1528, 1492, 1481, 1263, 1094 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₉ H ₃₃ F ₂ N ₂ O ₇ , 560.2283; found 560,2285 ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.05 (s, 1H), 8.32 (d, J=7.9 Hz, 1H), 7.98 (d, J=5.2 Hz, 1H ), 7.43 (dd, J=8.7, 5.6 Hz, 1H), 7.23 (dd, J=8.7, 5.6 Hz, 1H), 7.11 (dd, J= 9.6, 2.8 Hz, 1H), 7.04 (dd, J=9.6, 2.8 Hz, 1H), 6.96-6.89 (m, 2H), 6.87 (d , J=5.2 Hz, 1H), 5.63 (dc, J=8.7, 6.2 Hz, 1H), 4.71 (d, J=8.8 Hz, 1H), 4.63 (d, J=12.4 Hz, 1H), 4.58-4.36 (m, 4H), 3.94 (s, 3H), 3.43 (s, 3H), 3.38 (s, 3H), 1.30 (d, J=6.2 Hz, 3H), 1.12 (d, J=7.2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -115.46, -115.76. 429

(Thin Film) 3369, 2975, 1736, 1649, 1527, 1481, 1262, 1093 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₁ H ₃₇ F ₂ N ₂ O ₇ , 587.2563; found 587,2559 ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.06 (s, 1H), 8.33 (d, J=7.9 Hz, 1H), 7.98 (d, J=5.2 Hz, 1H ), 7.45 (dd, J=8.7, 5.6 Hz, 1H), 7.21 (dd, J=8.7, 5.6 Hz, 1H), 7.12 (dd, J= 9.6, 2.8 Hz, 1H), 7.07 (dd, J=9.7, 2.8 Hz, 1H), 6.94-6.84 (m, 3H), 5.73-5 .56 (m, 1H), 4.78-4.63 (m, 2H), 4.60-4.38 (m, 4H), 3.94 (s, 3H), 3.62-3.42 (m, 4H), 1.33-1.25 (m, 6H), 1.23 (t, J=7.0 Hz, 3H), 1.12 (d, J=7.2 Hz, 3H) .
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -115.57, -115.85. 430

HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₆ H ₂₈ FN ₂ O ₆ , 483.1931; found 483,1928 ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.11 (s, 1H), 8.35 (d, J=8.0 Hz, 1H), 7.97 (d, J=5.3 Hz, 1H ), 7.48-7.07 (m, 6H), 6.85 (d, J=5.3 Hz, 1H), 6.58 (t, J=8.3 Hz, 2H), 5.85 (dd, J=10.1, 6.0 Hz, 1H), 4.72-4.38 (m, 2H), 3.93 (s, 3H), 3.83 (s, 3H), 1, 25 (d, J=6.2 Hz, 3H), 0.99 (d, J=7.2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -113.13. 431

HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₆ H ₂₈ FN ₂ O ₅ , 467.1982; found 467,1976 ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.09 (s, 1H), 8.33 (d, J=7.9 Hz, 1H), 7.97 (d, J=5.2 Hz, 1H ), 7.36-7.07 (m, 6H), 6.94-6.78 (m, 3H), 5.78 (dc, J=10.4, 6.1 Hz, 1H), 4, 52 (n, J=7.3 Hz, 1H), 4.29 (d, J=10.3 Hz, 1H), 3.93 (s, 3H), 2.39 (s, 3H), 1, 28 (d, J=6.1 Hz, 3H), 1.00 (d, J=7.2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -116.60. 432

HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₆ H ₂₈ FN ₂ O ₆ , 483.1931; found 483,1931 ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.09 (s, 1H), 8.34 (d, J=8.0 Hz, 1H), 7.97 (d, J=5.2 Hz, 1H ), 7.47-7.20 (m, 5H), 7.20-7.10 (m, 1H), 6.86 (d, J=5.2 Hz, 1H), 6.57 (td, J=8.3, 2.6 Hz, 1H), 6.49 (dd, J=10.9, 2.5 Hz, 1H), 5.83 (dc, J=10.2, 6.1 Hz , 1H), 4.61-4.49 (m, 2H), 3.94 (s, 3H), 3.76 (s, 3H), 1.24 (d, J=6.1 Hz, 3H) , 1.07 (d, J=7.2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -113.49. 433

HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₆ H ₂₈ FN ₂ O ₅ , 467.1982; found 467,1974 ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.07 (s, 1H), 8.34 (d, J=8.0 Hz, 1H), 7.97 (d, J=5.2 Hz, 1H ), 7.35 (dd, J=8.7, 5.7 Hz, 1H), 7.31-7.13 (m, 5H), 6.92-6.80 (m, 2H), 6, 76 (dd, J=9.7, 2.8 Hz, 1H), 5.75 (dc, J=10.1, 6.1 Hz, 1H), 4.53 (p, J=7.3 Hz , 1H), 4.26 (d, J=10.1 Hz, 1H), 3.93 (s, 3H), 2.30 (s, 3H), 1.26 (d, J=6.1 Hz , 3H), 1.05 (d, J=7.2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -116.99. 434

HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₇ H ₃₀ FN ₂ O ₆ , 497.2088; found 497,2077 ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.12 (s, 1H), 8.35 (d, J=8.0 Hz, 1H), 7.98 (d, J=5.2 Hz, 1H ), 7.19 (d, J=8.0 Hz, 2H), 7.17-7.08 (m, 1H), 7.01 (d, J=8.0 Hz, 2H), 6.86 (d, J=5.2 Hz, 1H), 6.64-6.51 (m, 2H), 5.82 (dc, J=9.9, 6.2 Hz, 1H), 4.63- 4.41(m, 2H), 3.94(s, 3H), 3.83(s, 3H), 2.25(s, 3H), 1.24(d, J=6.2Hz, 3H ), 1.03 (d, J=7.2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -113.38. 435

HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₇ H ₃₀ FN ₂ O ₅ , 481.2139; found 481,2133 ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.11 (s, 1H), 8.34 (d, J=8.0 Hz, 1H), 7.98 (d, J=5.2 Hz, 1H ), 7.38-7.26 (m, 1H), 7.13 (d, J=8.1 Hz, 2H), 7.00 (d, J=8.0 Hz, 2H), 6.95 -6.80 (m, 3H), 5.76 (dc, J=10.2, 6.2 Hz, 1H), 4.53 (n, J=7.3 Hz, 1H), 4.25 ( d, J=10.2 Hz, 1H), 3.93 (s, 3H), 2.38 (s, 3H), 2.24 (s, 3H), 1.27 (d, J=6.1 Hz, 3H), 1.04 (d, J=7.2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -116.80. 436

HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₇ H ₃₀ FN ₂ O ₆ , 497.2088; found 497,2076 ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.10 (s, 1H), 8.34 (d, J=8.0 Hz, 1H), 7.97 (d, J=5.2 Hz, 1H ), 7.33-7.22 (m, 1H), 7.19-7.13 (m, 2H), 7.06 (d, J=7.8 Hz, 2H), 6.85 (d, J=5.2Hz, 1H), 6.56(td, J=8.3, 2.6Hz, 1H), 6.48(dd, J=10.9, 2.5Hz, 1H), 5.80 (dc, J=10.4, 6.1 Hz, 1H), 4.62-4.44 (m, 2H), 3.94 (s, 3H), 3.76 (s, 3H) , 2.28 (s, 3H), 1.23 (d, J=6.1 Hz, 3H), 1.06 (d, J=7.2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -113.69. 437

HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₇ H ₃₀ FN ₂ O ₅ , 481.2139; found 481,2121 ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.07 (s, 1H), 8.33 (d, J=8.0 Hz, 1H), 7.97 (d, J=5.2 Hz, 1H ), 7.33 (dd, J=8.7, 5.8 Hz, 1H), 7.18-7.00 (m, 4H), 6.94-6.81 (m, 2H), 6, 74 (dd, J=9.7, 2.8 Hz, 1H), 5.73 (dc, J=10.1, 6.1 Hz, 1H), 4.52 (n, J=7.3 Hz , 1H), 4.22 (d, J=10.3 Hz, 1H), 3.94 (s, 3H), 2.29 (s, 3H), 2.28 (s, 3H), 1.25 (d, J=6.1 Hz, 3H), 1.04 (d, J=7.2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -117.22. 438

HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₆ H ₂₇ F ₂ N ₂ O ₆ , 501.1837; found 501,1829 ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.09 (s, 1H), 8.33 (d, J=8.0 Hz, 1H), 7.98 (d, J=5.2 Hz, 1H ), 7.31-7.23 (m, 2H), 7.12 (dd, J=8.2, 6.5 Hz, 1H), 6.94-6.80 (m, 3H), 6, 64-6.52 (m, 2H), 5.81 (dc, J=10.0, 6.2 Hz, 1H), 4.61-4.38 (m, 2H), 3.94 (s, 3H), 3.83 (s, 3H), 1.25 (d, J=6.2 Hz, 3H), 1.06 (d, J=7.2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -112.82, -116.36. 439

HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₆ H ₂₇ F ₂ N ₂ O ₅ , 485.1888; found 485,1874 ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.08 (s, 1H), 8.33 (d, J=7.9 Hz, 1H), 7.97 (d, J=5.2 Hz, 1H ), 7.33-7.12 (m, 3H), 6.97-6.83 (m, 5H), 5.73 (dc, J=9.9, 6.1 Hz, 1H), 4, 68-4.46 (m, 1H), 4.28 (d, J=10.1 Hz, 1H), 3.94 (s, 3H), 2.36 (s, 3H), 1.28 (d , J=6.1 Hz, 3H), 1.09 (d, J=7.2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -115.88, -116.28. 440

HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₆ H ₂₇ F ₂ N ₂ O ₆ , 501.1837; found 501,1824 ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.08 (s, 1H), 8.33 (d, J=8.0 Hz, 1H), 7.97 (d, J=5.2 Hz, 1H ), 7.30-7.19 (m, 3H), 6.99-6.90 (m, 2H), 6.86 (d, J=5.3 Hz, 1H), 6.57 (td, J=8.3, 2.5 Hz, 1H), 6.50 (dd, J=10.9, 2.5 Hz, 1H), 5.92-5.68 (m, 1H), 4.64 -4.40 (m, 2H), 3.94 (s, 3H), 3.76 (s, 3H), 1.23 (d, J=6.2 Hz, 3H), 1.09 (d, J=7.2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -113.15, -116.03. 441

HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₆ H ₂₇ F ₂ N ₂ O ₅ , 485.1888; found 485,1876 ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.06 (s, 1H), 8.34 (d, J=8.0 Hz, 1H), 7.96 (d, J=5.2 Hz, 1H ), 7.33 (dd, J=8.7, 5.7 Hz, 1H), 7.19 (dd, J=8.5, 5.4 Hz, 2H), 7.02-6.90 ( m, 2H), 6.91-6.82 (m, 2H), 6.77 (dd, J=9.7, 2.8 Hz, 1H), 5.71 (dc, J=9.8, 6.1 Hz, 1H), 4.53 (n, J=7.3 Hz, 1H), 4.26 (d, J=9.9 Hz, 1H), 3.93 (s, 3H), 2 .27 (s, 3H), 1.25 (d, J=6.2 Hz, 3H), 1.07 (d, J=7.2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -115.42, -116.65. 442

(Thin Film) 3376, 2929, 1736, 1650, 1576, 1529, 1481, 1452 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₇ H ₃₁ N ₂ O ₅ , 463.2224; found 463,2227 ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.11 (s, 1H), 8.35 (d, J=8.0 Hz, 1H), 7.98 (d, J=5.2 Hz, 1H ), 7.20-7.13 (m, 1H), 7.12-7.06 (m, 5H), 7.03-6.97 (m, 1H), 6.96-6.92 (m , 1H), 6.85 (d, J=5.2 Hz, 1H), 5.79 (dc, J=10.3, 6.1 Hz, 1H), 4.57-4.44 (m, 1H), 3.97 (d, J=10.4 Hz, 1H), 3.93 (s, 3H), 2.31 (s, 3H), 2.27 (s, 3H), 1.25 ( d, J=6.1 Hz, 3H), 0.97 (d, J=7.2 Hz, 3H). 443

HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₇ H ₂₉ F ₂ N ₂ O ₆ , 516.2021; found 516,2018 ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.09 (s, 1H), 8.35 (d, J=7.7 Hz, 1H), 7.97 (d, J=5.2 Hz, 1H ), 7.23 (dd, J=8.5, 6.6 Hz, 1H), 7.17 (dd, J=8.6, 5.8 Hz, 1H), 6.90-6.73 ( m, 2H), 6.57 (td, J=8.3, 2.5 Hz, 1H), 6.49 (dd, J=10.8, 2.5 Hz, 1H), 5.70 (dc , J=10.1, 6.1 Hz, 2H), 4.75 (d, J=10.2 Hz, 1H), 4.55 (n, J=7.3 Hz, 1H), 3.94 (s, 3H), 3.76 (s, 3H), 2.43 (s, 3H), 1.24 (d, J=6.2 Hz, 3H), 1.12 (d, J=7, 2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -113.36, -116.89. 444

HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₆ H ₂₆ F ₃ N ₂ O ₆ , 519.1737; found 519,1734 ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.07 (s, 1H), 8.33 (d, J=7.9 Hz, 1H), 7.97 (d, J=5.2 Hz, 1H ), 7.29 (dd, J=8.4, 6.7 Hz, 1H), 7.25-7.14 (m, 1H), 6.86 (d, J=5.2 Hz, 1H) , 6.81-6.70 (m, 2H), 6.56 (td, J=8.3, 2.5 Hz, lH), 6.50 (dd, J=10.8, 2.5 Hz , 1H), 5.82 (dc, J=11.5, 6.2 Hz, 1H), 4.78 (d, J=10.1 Hz, 1H), 4.55 (n, J=7, 2 Hz, 1H), 3.94 (s, 3H), 3.75 (s, 3H), 1.26 (d, J=6.1 Hz, 3H), 1.12 (d, J=7, 2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) 8-112.12 (d, J=7.5 Hz), -112.18 (d, J=7.5 Hz), -112.75 445

HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₇ H ₂₉ F ₂ N ₂ O ₆ , 516.2021; found 516,2021 ¹ H NMR (400 MHz, CDCl ₃ ) 5 12.08 (s, 1H), 8.33 (d, J=7.9 Hz, 1H), 7.97 (d, J=5.2 Hz, 1H ), 7.32 (dd, J=8.6, 5.8 Hz, 1H), 7.03 (dd, J=8.3, 6.7 Hz, 1H), 6.86 (d, J= 5.2 Hz, 1H), 6.81 (td, J=8.5, 2.8 Hz, 1H), 6.75 (dd, J=9.7, 2.7 Hz, 1H), 6, 62-6.51 (m, 2H), 5.69 (dc, J=10.0, 6.2 Hz, 1H), 4.76 (d, J=9.8 Hz, 1H), 4.53 (n, J=7.2 Hz, 1H), 3.94 (s, 3H), 3.84 (s, 3H), 2.26 (s, 3H), 1.27 (d, J=6, 2 Hz, 3H), 1.07 (d, J=7.2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -112.84, -117.29. 446

HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₆ H ₂₆ F ₃ N ₂ O ₅ , 504.1821; found 504,1818 ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.04 (s, 1H), 8.31 (d, J=7.8 Hz, 1H), 7.97 (d, J=5.2 Hz, 1H ), 7.32 (dd, J=8.6, 5.7 Hz, 1H), 7.18-7.07 (m, 1H), 6.90-6.72 (m, 5H), 5, 70 (dc, J=11.7, 6.4 Hz, 1H), 4.64 (d, J=10.0 Hz, 1H), 4.54 (p, J=7.2 Hz, 1H), 3.94 (s, 3H), 2.27 (s, 3H), 1.29 (d, J=6.1 Hz, 3H), 1.09 (d, J=7.2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -111.40 (d, J=7.6 Hz), -112.58 (d, J=7.6 Hz), -116.32. 447

(Thin Film) 3373, 2980, 2938, 1737, 1650, 1576, 1530, 1481, 1452 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₆ H ₂₈ FN ₂ O ₅ , 467.1977; found 467,1974 ¹ H NMR (400 MHz, CDCl ₃ ) 5 12.30-12.00 (m, 1H), 8.36 (d, J=8.0 Hz, 1H), 7.96 (dd, J=5, 2, 1.5 Hz, 1H), 7.39-7.12 (m, 6H), 6.89-6.82 (m, 2H), 6.72 (dd, J=11.3, 1, 6 Hz, 1H), 5.82 (dc, J=9.8, 6.0 Hz, 1H), 4.56 (n, J=7.3 Hz, 1H), 4.41 (d, J= 10.1 Hz, 1H), 3.92 (s, 3H), 2.23 (s, 3H), 1.26 (d, J=6.1 Hz, 3H), 1.09 (d, J= 7.2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -118.95. 448

(Thin Film) 3377, 2983, 1737, 1650, 1577, 1530, 1510, 1481, 1453, 1440 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₆ H ₂₇ F ₂ N ₂ O ₅ , 485.1883; found 485,1877 ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.07 (d, J=0.6 Hz, 1H), 8.34 (d, J=8.0 Hz, 1H), 7.98 (d, J =5.2Hz, 1H), 7.29-7.23(m, 2H), 7.21(t, J=7.9Hz, 1H), 7.00-6.93(m, 2H) , 6.89-6.84 (m, 2H), 6.75-6.71 (m, 1H), 5.81-5.68 (m, 1H), 4.60-4.49 (m, 1H), 4.39 (d, J=10.1 Hz, 1H), 3.94 (s, 3H), 2.24 (s, 3H), 1.26 (d, J=6.1 Hz, 3H), 1.10 (d, J=7.2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -115.56, -118.95. 449

(Thin Film) 3378, 2982, 2932, 1738, 1650, 1576, 1530, 1481, 1452 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₇ H ₃₀ FN ₂ O ₅ , 481.2133; found 481,2133 ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.10 (s, 1H), 8.36 (d, J=8.0 Hz, 1H), 7.97 (d, J=5.1 Hz, 1H ), 7.28-7.12 (m, 3H), 7.08 (d, J=7.8 Hz, 2H), 6.88-6.81 (m, 2H), 6.71 (d, J=11.2 Hz, 1H), 5.80 (dc, J=12.1, 6.2 Hz, 1H), 4.55 (n, J=7.3 Hz, 1H), 4.38 ( d, J=10.1 Hz, 1H), 3.92 (s, 3H), 2.28 (s, 3H), 2.22 (s, 3H), 1.26 (d, J=6.1 Hz, 3H), 1.09 (d, J=7.0 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -119.09. 450

(Thin film) 3373, 2982, 1737, 1651, 1577, 1530, 1482, 1453 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₇ H ₂₉ F ₂ N ₂ O ₅ , 499.2039; found 499,2033 ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.09 (d, J=0.6 Hz, 1H), 8.34 (d, J=8.0 Hz, 1H), 7.98 (d, J =5.2 Hz, 1H), 7.24 (dd, J=9.4, 5.5 Hz, 1H), 7.15 (t, J=7.9 Hz, 1H), 6.90-6 .78 (m, 4H), 6.75-6.67 (m, 1H), 5.79-5.68 (m, 1H), 4.64 (d, J=10.2 Hz, 1H), 4.61-4.52 (m, 1H), 3.94 (s, 3H), 2.39 (s, 3H), 2.24 (s, 3H), 1.27 (d, J=6, 2 Hz, 3H), 1.13 (d, J=7.2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -116.44, -118.17. 451

(Thin Film) 3375, 2982, 2939, 1739, 1651, 1577, 1530, 1504, 1481, 1453 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₆ H ₂₆ F ₃ N ₂ O ₅ , 503.1788; found 503,1784 ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.06 (s, 1H), 8.33 (d, J=8.0 Hz, 1H), 7.98 (d, J=5.2 Hz, 1H ), 7.32-7.20 (m, 2H), 6.91-6.70 (m, 5H), 5.86-5.76 (m, 1H), 4.70 (d, J=10 .0 Hz, 1H), 4.62-4.51 (m, 1H), 3.94 (s, 3H), 2.25 (s, 3H), 1.29 (d, J=6.2 Hz , 3H), 1.12 (d, J=7.3 Hz, 3H). 452

HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₆ H ₂₈ FN ₂ O ₅ , 467.1982; found 467,1969 ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.08 (d, J=0.6 Hz, 1H), 8.33 (d, J=8.0 Hz, 1H), 7.98 (d, J =5.2 Hz, 1H), 7.31-7.19 (m, 4H), 7.17-7.12 (m, 1H), 7.12-7.02 (m, 2H), 6, 91 (dd, J=9.3, 8.3 Hz, 1H), 6.86 (d, J=5.2 Hz, 1H), 5.77 (dc, J=10.2, 6.1 Hz , 1H), 4.59-4.46 (m, 1H), 3.99 (d, J=10.2 Hz, 1H), 3.94 (s, 3H), 2.23 (d, J= 1.9 Hz, 3H), 1.25 (d, J=6.2 Hz, 3H), 0.97 (d, J=7.2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -120.09. 453

HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₇ H ₂₉ F ₂ N ₂ O ₆ , 515.1993; found 515,1980 ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.08 (s, 1H), 8.33 (d, J=8.0 Hz, 1H), 7.97 (d, J=5.2 Hz, 1H ), 7.25-7.20 (m, 1H), 7.12-7.01 (m, 2H), 6.93-6.82 (m, 2H), 6.57 (td, J=8 .3, 2.5 Hz, 1H), 6.50 (dd, J=10.9, 2.5 Hz, 1H), 5.76 (dc, J=10.3, 6.1 Hz, 1H) , 4.61-4.48 (m, 1H), 4.45 (d, J=10.2 Hz, 1H), 3.94 (s, 3H), 3.77 (s, 3H), 2, 22 (d, J=1.9 Hz, 3H), 1.22 (d, J=6.1 Hz, 3H), 1.07 (d, J=7.2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -113.33, -120.33. 454

(Thin Film) 3373, 2980, 2938, 1735, 1649, 1576, 1528, 1495, 1480, 1451, 1332, 1280, 1263, 1242, 1213, 1144, 1048, 799, 733, 69 9 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₆ H ₂₉ N ₂ O ₅ , 449.2071; found 449,2063 ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.10 (d, J=0.6 Hz, 1H), 8.34 (d, J=8.0 Hz, 1H), 7.98 (d, J =5.2 Hz, 1H), 7.31-7.27 (m, 2H), 7.24-7.15 (m, 4H), 7.15-7.06 (m, 3H), 6, 86 (d, J=5.2 Hz, 1H), 5.81 (dc, J=10.2, 6.1 Hz, 1H), 4.57-4.46 (m, 1H), 4.02 (d, J=10.2 Hz, 1H), 3.94 (s, 3H), 2.28 (s, 3H), 1.26 (d, J=6.1 Hz, 3H), 0.96 (d, J=7.2 Hz, 3H).
¹³ C NMR (126 MHz, CDCl ₃ ) δ 171.68, 168.51, 155.33, 148.70, 141.68, 140.40, 138.15, 136.55, 130.48, 129.48 , 128.48, 127.93, 126.59, 109.38, 73.63, 57.57, 56.07, 47.85, 20.98, 19.24, 17.61. 455

(Thin Film) 3367, 2981, 2938, 1736, 1649, 1576, 1529, 1480, 1451, 1333, 1281, 1263, 1213, 1146, 1048, 801, 734, 700 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₆ H ₂₉ N ₂ O ₅ , 449.2071; found 449,2068 ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.11 (d, J=0.6 Hz, 1H), 8.35 (d, J=8.0 Hz, 1H), 7.98 (d, J =5.2 Hz, 1H), 7.29-7.24 (m, 4H), 7.20-7.15 (m, 3H), 7.03 (d, J=7.9 Hz, 2H) , 6.86 (d, J=5.2 Hz, 1H), 5.80 (dc, J=10.1, 6.2 Hz, 1H), 4.58-4.47 (m, 1H), 4.02 (d, J=10.0 Hz, 1H), 3.94 (s, 3H), 2.25 (s, 3H), 1.25 (d, J=6.1 Hz, 3H), 1.01 (d, J=7.2 Hz, 3H).
¹³ C NMR (126 MHz, CDCl ₃ ) δ 171.65, 168.50, 155.33, 148.69, 141.41, 140.38, 138.28, 136.20, 130.47, 129.12 , 128.74, 128.05, 127.90, 126.82, 109.36, 73.61, 57.44, 56.06, 47.86, 20.92, 19.23, 17.67. 456

(Thin Film) 3369, 2982, 2937, 1735, 1649, 1576, 1528, 1508, 1480, 1451, 1329, 1280, 1263, 1218, 1157, 1049, 815, 800, 729 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₆ H ₂₈ FN ₂ O ₅ , 467.1977; found 467,1974 ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.09 (s, 1H), 8.34 (d, J=8.0 Hz, 1H), 7.98 (d, J=5.2 Hz, 1H ), 7.25-7.21 (m, 2H), 7.18-7.13 (m, 2H), 7.04 (d, J=7.9 Hz, 2H), 7.00-6, 92 (m, 2H), 6.86 (d, J=5.2 Hz, 1H), 5.75 (dc, J=9.9, 6.2 Hz, 1H), 4.59-4.47 (m, 1H), 4.02 (d, J=9.8 Hz, 1H), 3.94 (s, 3H), 2.26 (s, 3H), 1.24 (d, J=6, 2 Hz, 3H), 1.02 (d, J=7.2 Hz, 3H).
¹³ C NMR (126 MHz, CDCl ₃ ) δ 171.61, 168.52, 161.66 (d, J=245.6 Hz), 155.35, 148.71, 140.40, 138.01, 137 .20 (d, J=3.3 Hz), 136.40, 130.44, 129.53 (d, J=7.9 Hz), 129.22, 127.84, 115.57 (d, J =21.1 Hz), 109.39, 73.44, 56.56, 56.07, 47.85, 20.92, 19.14, 17.66. 457

(Thin Film) 3373, 2982, 2938, 1736, 1649, 1576, 1529, 1509, 1480, 1452, 1330, 1280, 1263, 1242, 1220, 1159, 1048, 815, 799, 73 2,699 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₅ H ₂₆ FN ₂ O ₅ , 453.1820; found 453,1810 ¹ H NMR (300 MHz, CDCl ₃ ) δ 12.07 (d, J=0.6 Hz, 1H), 8.33 (d, J=8.0 Hz, 1H), 7.98 (d, J =5.2 Hz, 1H), 7.33-7.19 (m, 7H), 6.96-6.88 (m, 2H), 6.87 (dd, J=5.3, 0.6 Hz, 1H), 5.78 (dc, J=9.9, 6.1 Hz, 1H), 4.61-4.47 (m, 1H), 4.05 (d, J=10.0 Hz , 1H), 3.94 (s, 3H), 1.26 (d, J=6.2 Hz, 3H), 1.05 (d, J=7.2 Hz, 3H).
¹³ C NMR (126 MHz, CDCl ₃ ) δ 171.62, 168.57, 161.59 (d, J=245.2 Hz), 155.38, 148.73, 140.92, 140.43, 137 .11 (d, J=3.5 Hz), 130.39, 129.53 (d, J=7.8 Hz), 128.88, 127.99, 127.08, 115.29 (d, J =21.2 Hz), 109.43, 73.50, 57.03, 56.08, 47.87, 19.21, 17.69. 458

(Thin film) 3366, 2979, 2939, 1736, 1649, 1576, 1529, 1509, 1481, 1451, 1332, 1264, 1242, 1220, 1159, 1049, 815, 800, 770, 732 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₆ H ₂₈ FN ₂ O ₅ , 467.1977; found 467,1969 ¹ H NMR (300 MHz, CDCl ₃ ) δ 12.08 (d, J=0.6 Hz, 1H), 8.33 (d, J=8.0 Hz, 1H), 7.98 (d, J =5.2Hz, 1H), 7.30-7.21(m, 2H), 7.14(d, J=8.3Hz, 2H), 7.09(d, J=8.2Hz , 2H), 6.95-6.84 (m, 3H), 5.76 (dc, J=10.1, 6.1 Hz, 1H), 4.59-4.47 (m, 1H), 4.01 (d, J=10.1 Hz, 1H), 3.94 (s, 3H), 2.29 (s, 3H), 1.25 (d, J=6.1 Hz, 3H), 1.04 (d, J=7.2 Hz, 3H).
¹³ C NMR (126 MHz, CDCl ₃ ) δ 171.61, 168.55, 161.53 (d, J=244.9 Hz), 155.37, 148.71, 140.41, 137.93, 137 .41 (d, J=3.3 Hz), 136.72, 130.39, 129.54, 129.41 (d, J=7.9 Hz), 127.82, 115.24 (d, J =21.3 Hz), 109.41, 73.55, 56.67, 56.07, 47.87, 20.96, 19.20, 17.68. 459

(Thin Film) 3376, 2984, 2938, 1737, 1649, 1576, 1529, 1503, 1481, 1452, 1327, 1281, 1263, 1243, 1212, 1146, 1050, 966, 849, 80 0.733.699 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₅ H ₂₅ F ₂ N ₂ O ₅ , 471.1726; found 471,1726 ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.07 (d, J=0.6 Hz, 1H), 8.32 (d, J=8.0 Hz, 1H), 7.98 (d, J =5.2 Hz, 1H), 7.35-7.20 (m, 5H), 7.19-7.10 (m, 1H), 6.88-6.75 (m, 3H), 5, 88-5.77 (m, 1H), 4.58-4.47 (m, 1H), 4.42 (d, J=10.1 Hz, 1H), 3.94 (s, 3H), 1 .29 (d, J=6.2 Hz, 3H), 1.00 (d, J=7.2 Hz, 3H).
¹³ C NMR (126 MHz, CDCl ₃ ) δ 171.56, 168.54, 162.05 (dd, J=172.5, 11.9 Hz), 161.09-159.28 (m), 155, 35, 148.72, 140.42, 140.02, 130.41, 130.23-129.63 (m), 128.61, 128.18, 127.03, 124.46-123.89 (m ), 111.63 (d, J=21.2 Hz), 109.41, 104.54-103.81 (m), 72.76, 56.08, 49.36, 47.83, 18.90 , 17.60. 460

(Thin Film) 3370, 2983, 2937, 1737, 1649, 1576, 1529, 1502, 1481, 1452, 1439, 1329, 1281, 1264, 1243, 1211, 1147, 1050, 966, 8 49, 801, 732 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₆ H ₂₇ F ₂ N ₂ O ₅ , 485.1883; found 485,1880 ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.08 (d, J=0.6 Hz, 1H), 8.33 (d, J=8.0 Hz, 1H), 7.98 (d, J =5.2 Hz, 1H), 7.26-7.21 (m, 1H), 7.20-7.15 (m, 2H), 7.07-7.01 (m, 2H), 6, 88-6.85(m, 1H), 6.84-6.74(m, 2H), 5.86-5.72(m, 1H), 4.59-4.48(m, 1H), 4.39 (d, J=9.9 Hz, 1H), 3.94 (s, 3H), 2.26 (s, 3H), 1.28 (d, J=6.3 Hz, 3H), 1.04 (d, J=7.2 Hz, 3H).
¹³ C NMR (126 MHz, CDCl ₃ ) δ 171.55, 168.53, 161.99 (dd, J=171.0, 11.9 Hz), 160.02 (dd, J=170.8, 11 .7 Hz), 155.36, 148.72, 140.41, 136.92, 136.63, 130.43, 129.97-129.69 (m), 129.24, 128.06, 124, 73 -124.42 (m), 111.58 (d, J=17.7 Hz), 109.40, 104.83-103.37 (m), 72.82, 56.08, 48.91, 47.85, 20.95, 18.90, 17.67. 461

(Thin Film) 3371, 2984, 2939, 1738, 1649, 1604, 1577, 1529, 1503, 1481, 1452, 1439, 1326, 1281, 1264, 1242, 1223, 1160, 1050, 966, 849, 810, 732 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₅ H ₂₄ F ₃ N ₂ O ₅ , 489.1632; found 489,1624 ¹ H NMR (400 MHz, CDCl ₃ ) δ 12.05 (d, J=0.6 Hz, 1H), 8.30 (d, J=8.0 Hz, 1H), 7.98 (d, J =5.2 Hz, 1H), 7.31-7.17 (m, 3H), 6.97-6.75 (m, 5H), 5.83-5.73 (m, 1H), 4, 59-4.49 (m, 1H), 4.40 (d, J=10.0 Hz, 1H), 3.95 (s, 3H), 1.28 (d, J=6.1 Hz, 3H ), 1.08 (d, J=7.2 Hz, 3H).
¹³ C NMR (126 MHz, CDCl ₃ ) δ 171.51, 168.59, 162.96-162.09 (m), 161.43-159.21 (m), 155.41, 148.74, 140 .45, 135.75, 130.33, 129.73 (d, J=8.0 Hz), 124.13 (dd, J=15.2, 3.7 Hz), 115.43 (d, J =21.3 Hz), 111.73 (d, J=25.0 Hz), 109.46, 104.30 (t, J=25.8 Hz), 72.66, 56.10, 48.70 , 47.86, 18.91, 17.67. 462

HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₈ H ₂₉ F ₂ N ₂ O ₇ , 543.1931; found 543,1937. ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.28 (d, J=5.4 Hz, 1H), 8.14 (d, J=7.8 Hz, 1H), 7.26-7.15 (m, 4H), 6.94 (dddd, J=24.3, 8.7, 6.9, 2.1 Hz, 5H), 5.76-5.63 (m, 3H), 4.55 (n, J=7.3 Hz, 1H), 4.05 (d, J=8.9 Hz, 1H), 3.92 (s, 3H), 2.06 (s, 3H), 1.32 (d, J=7.1 Hz, 3H), 1.22 (d, J=6.2 Hz, 3H).
¹³ C NMR (101 MHz, CDCl ₃ ) δ 171.92, 170.28, 162.91, 162.81, 162.77, 160.46, 160.37, 145.63, 144.13, 142.28 136.93 136.90 136.54 136.51 129.82 129.74 129.70 129.62 115.72 115.51 115.43 115.22 109 .60, 89.60, 73.10, 56.20, 55.58, 48.04, 20.85, 20.81, 18.94, 18.05. 463

HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₈ H ₂₉ F ₂ N ₂ O ₇ , 543.1931; found 543,1937. ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.26 (d, J=5.4 Hz, 1H), 8.20 (d, J=7.9 Hz, 1H), 7.28-7.17 (m, 4H), 7.02-6.89 (m, 5H), 5.76-5.66 (m, 3H), 4.55 (n, J=7.3 Hz, 1H), 4, 04 (d, J=9.7 Hz, 1H), 3.90 (s, 3H), 2.05 (s, 3H), 1.23 (d, J=6.1 Hz, 3H), 0, 99 (d, J=7.2 Hz, 3H).
¹³ C NMR (101 MHz, CDCl ₃ ) δ 172.24, 170.26, 162.95, 162.90, 162.86, 160.51, 160.42, 160.28, 145.68, 143.98 142.41 136.94 136.91 136.86 136.82 129.62 129.57 129.54 129.49 115.79 115.58 115.49 115 .28, 109.58, 89.51, 73.04, 56.18, 56.13, 48.05, 20.85, 19.14, 17.81. 464

(Thin Film) 3378, 2984, 1738, 1676, 1496, 1202, 1003, 729 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₀ H ₃₃ F ₂ N ₂ O ₇ , 571.2250; found 571,2265 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.26 (d, J=5.3 Hz, 1H), 8.21 (d, J=7.9 Hz, 1H), 7.26-7.22 (m, 1H), 7.14 (dd, J=8.6, 5.8 Hz, 1H), 6.94 (d, J=5.4 Hz, 1H), 6.89-6.77 ( m, 4H), 5.73 (s, 2H), 5.62 (dc, J=9.1, 6.2 Hz, 1H), 4.56 (n, J=7.2 Hz, 1H), 4.44 (d, J=9.8 Hz, 1H), 3.91 (s, 3H), 2.38 (s, 3H), 2.33 (s, 3H), 2.06 (s, 3H ), 1.30 (d, J=6.2 Hz, 3H), 1.04 (d, J=7.2 Hz, 3H).
¹³ C NMR (101 MHz, CDCl ₃ ) δ 172.30, 170.26, 162.91, 161.19 (d, J=245.6 Hz), 161.10 (d, J=245.0 Hz) , 160.28, 145.70, 143.98, 142.43, 139.12 (d, J=7.4 Hz), 138.81 (d, J=7.5 Hz), 134.89 (d , J=3.3 Hz), 134.39 (d, J=3.2 Hz), 129.37 (d, J=8.2 Hz), 128.75 (d, J=8.3 Hz) , 117.41 (d, J=20.9 Hz), 117.10 (d, J=20.9 Hz), 112.94 (d, J=20.9 Hz), 112.63 (d, J =20.8Hz), 109.59, 89.52, 74.29, 56.19, 48.07, 46.40, 20.86, 20.20, 20.12, 18.82, 17.86 .
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -116.57, -117.03. 465

(Thin Film) 3379, 2962, 1737, 1676, 1506, 1201, 1004, 729 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₆ H ₄₇ N ₂ O ₇ , 619.3378; found 619.3388 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.26 (d, J=5.4 Hz, 1H), 8.23 (d, J=7.8 Hz, 1H), 7.32-7.20 (m, 8H), 6.93 (d, J=5.4 Hz, 1H), 5.79 (dc, J=10.2, 6.1 Hz, 1H), 5.73-5.70 ( m, 2H), 4.50 (n, J=7.2 Hz, 1H), 3.98 (d, J=10.2 Hz, 1H), 3.89 (s, 3H), 2.05 ( s, 3H), 1.27-1.22 (m, 21H), 0.78 (d, J=7.2 Hz, 3H).
¹³ C NMR (101 MHz, CDCl ₃ ) δ 172.43, 170.23, 162.84, 160.24, 149.56, 149.37, 145.69, 143.91, 142.62, 138.80 , 138.26, 127.69, 127.65, 125.60, 125.33, 109.49, 89.55, 73.71, 57.25, 56.15, 48.04, 34.36, 34 .31, 31.30, 20.85, 19.34, 17.50. 466

(Thin Film) 3378, 2959, 1737, 1676, 1506, 1202, 1044, 1004, 828, 731 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₄ H ₄₃ N ₂ O ₇ , 591.3065; found 591,3077 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.26 (d, J=5.4 Hz, 1H), 8.22 (d, J=7.8 Hz, 1H), 7.28-7.19 (m, 4H), 7.16-7.06 (m, 4H), 6.93 (d, J=5.4 Hz, 1H), 5.78 (dc, J=10.2, 6.1 Hz, 1H), 5.72 (d, J=0.9 Hz, 2H), 4.51 (n, J=7.2 Hz, 1H), 3.98 (d, J=10.2 Hz, 1H), 3.89 (s, 3H), 2.81 (dh, J=10.6, 6.9 Hz, 2H), 2.05 (s, 3H), 1.24 (d, J=6 .1 Hz, 3H), 1.18 (dd, J=13.6, 6.9 Hz, 12H), 0.81 (d, J=7.2 Hz, 3H).
¹³ C NMR (101 MHz, CDCl ₃ ) δ 172.42, 170.24, 162.85, 160.24, 147.29, 147.13, 145.69, 143.92, 142.63, 139.19 , 138.71, 127.95, 127.92, 126.75, 126.48, 109.49, 89.55, 73.66, 57.39, 56.16, 48.05, 33.65, 33 .61, 23.99, 23.97, 23.93, 20.86, 19.33, 17.57. 467

(Thin Film) 3388, 2979, 1756, 1677, 1503, 1203, 1044, 1004, 970, 731 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₂ H ₃₉ N ₂ O ₇ , 563.2752; found 563,2764 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.27 (d, J=5.3 Hz, 1H), 8.23 (d, J=7.8 Hz, 1H), 7.07-6.90 (m, 7H), 5.82-5.67 (m, 3H), 4.54 (n, J=7.2 Hz, 1H), 3.90 (s, 3H), 2.17 (t, J=11.4Hz, 12H), 2.06(s, 3H), 1.28-1.20(m, 4H), 0.93(d, J=7.2Hz, 3H).
¹³ C NMR (101 MHz, CDCl ₃ ) δ 172.41, 170.25, 162.84, 160.23, 145.69, 143.90, 142.67, 139.25, 139.11, 136.78 , 136.34, 134.93, 134.51, 129.90, 129.62, 129.39, 129.38, 125.30, 125.08, 109.48, 89.55, 73.49, 57 .11, 56.16, 48.12, 20.86, 19.87, 19.80, 19.32, 19.29, 19.24, 17.80. 468

ESIMS m/z 541.2 ([M+H] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.41 (d, J=7.7 Hz, 1H), 8.30 (d, J=5.4 Hz, 1H), 7.32-7.21 (m, 1H), 7.14 (dd, J=8.5, 5.8 Hz, 1H), 6.99 (d, J=5.5 Hz, 1H), 6.83 (dd, J= 15.6, 10.1, 7.6 Hz, 4H), 5.62 (dc, J=9.6, 6.1 Hz, 1H), 4.62-4.50 (m, 1H), 4 .43 (d, J=9.7 Hz, 1H), 3.88 (s, 3H), 2.38 (s, 3H), 2.36 (s, 3H), 2.31 (s, 3H) , 1.29 (d, J=6.2 Hz, 3H), 1.03 (d, J=7.2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -116.52, -116.96. 469

(Thin film) 3379, 2962, 1772, 1677, 1508, 1198, 731 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₅ H ₄₅ N ₂ O ₆ , 589.3272; found 589,3289 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.43 (d, J=7.9 Hz, 1H), 8.32 (d, J=5.4 Hz, 1H), 7.26 (d, J =12.1 Hz, 8H), 6.98 (d, J=5.4 Hz, 1H), 5.78 (dc, J=10.1, 6.1 Hz, 1H), 4.56-4 .43 (m, 1H), 3.97 (d, J=10.2 Hz, 1H), 3.88 (s, 3H), 2.37 (s, 3H), 1.25 (d, J= 12.6 Hz, 21H), 0.77 (d, J=7.2 Hz, 3H).
¹³ C NMR (101 MHz, CDCl ₃ ) δ 172.32, 168.88, 162.23, 159.40, 149.55, 149.37, 146.64, 141.60, 138.76, 138.25 , 137.43, 127.70, 127.65, 125.60, 125.32, 109.67, 73.75, 57.22, 56.25, 47.81, 34.35, 34.31, 31 .31, 31.30, 20.73, 19.32, 17.69. 470

(Thin Film) 3379, 2960, 1772, 1677, 1509, 1201, 1175, 1047, 731 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₃ H ₄₁ N ₂ O ₆ , 561.2959; found 561,2977 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.42 (d, J=7.6 Hz, 1H), 8.32 (d, J=5.5 Hz, 1H), 7.22 (dd, J =8.3, 2.5 Hz, 4H), 7.15-7.04 (m, 4H), 6.98 (d, J=5.5 Hz, 1H), 5.78 (dc, J= 10.1, 6.1 Hz, 1H), 4.54-4.43 (m, 1H), 3.97 (d, J=10.2 Hz, 1H), 3.89 (s, 3H), 2.82 (dp, J=11.9, 6.9 Hz, 2H), 2.37 (s, 3H), 1.23 (d, J=6.2 Hz, 3H), 1.18 (dd , J=14.7, 6.9 Hz, 12H), 0.80 (d, J=7.2 Hz, 3H).
¹³ C NMR (101 MHz, CDCl ₃ ) δ 172.31, 168.89, 162.23, 159.41, 147.28, 147.13, 146.64, 141.61, 139.14, 138.70 , 137.43, 127.96, 127.92, 126.75, 126.47, 109.68, 73.70, 57.36, 56.25, 47.83, 33.64, 33.61, 23 .97, 23.93, 20.74, 19.31, 17.75. 471

(Thin Film) 3379, 2978, 1771, 1676, 1505, 1450, 1310, 1199, 1050, 907, 730 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₁ H ₃₇ N ₂ O ₆ , 533.2646; found 533.2659 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.48-8.37 (m, 1H), 8.32 (d, J=5.4 Hz, 1H), 7.09-6.90 (m, 7H), 5.74 (dc, J=10.0, 6.1 Hz, 1H), 4.58-4.46 (m, 1H), 3.98-3.83 (m, 4H), 2 .38 (s, 3H), 2.17 (dd, J=12.4, 11.0 Hz, 12H), 1.22 (d, J=6.1 Hz, 3H), 0.92 (d, J=7.1 Hz, 3H). 472

(Thin film) 3382, 2982, 1737, 1677, 1501, 1202 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₀ H ₃₃ F ₂ N ₂ O ₉ , 603.2149; found 603.2163 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.26 (d, J=5.4 Hz, 1H), 8.22 (d, J=7.9 Hz, 1H), 7.38 (m, 1H ), 7.13 (m, 1H), 6.94 (d, J=5.4 Hz, 1H), 6.61-6.47 (m, 4H), 5.87 (dc, J=9, 7, 6.2 Hz, 1H), 5.72 (s, 2H), 4.84 (d, J=9.6 Hz, 1H), 4.64-4.48 (m, 1H), 3, 90 (s, 3H), 3.82 (s, 3H), 3.74 (s, 3H), 2.06 (s, 3H), 1.22 (d, J=6.2 Hz, 3H), 1.03 (d, J=7.2 Hz, 3H). 473

(Thin Film) 3367, 2985, 1749, 1694, 1506, 1201, 1130, 828 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₈ H ₂₆ F ₅ N ₂ O ₇ , 597.1655; found 597,1672 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.77-8.42 (m, 1H), 8.42-8.15 (m, 1H), 7.26-7.15 (m, 4H), 7.06-6.86(m, 5H), 5.84-5.66(m, 3H), 5.37-5.19(m, 1H), 4.13-4.03(m, 1H ), 4.04-3.83 (m, 3H), 2.09-1.99 (m, 3H), 1.30-1.16 (m, 3H). 474

HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₉ H ₃₃ N ₂ O ₇ , 521.2282; found 521,2292. ¹ H NMR (300 MHz, CDCl ₃ ) δ 8.28 (t, J=7.2 Hz, 2H), 7.35-7.12 (m, 10H), 6.94 (d, J=5, 4 Hz, 1H), 5.86 (k, J=6.3 Hz, 1H), 5.75-5.68 (m, 2H), 4.62 (p, J=7.2 Hz, 1H) , 3.90 (s, 3H), 2.06 (s, 3H), 1.75 (s, 3H), 1.16 (d, J=6.3 Hz, 3H), 1.12 (d, J=7.2 Hz, 3H).
¹³ C NMR (101 MHz, CDCl ₃ ) δ 172.27, 170.20, 162.88, 160.26, 146.57, 145.66, 145.11, 143.98, 142.56, 128.18 , 128.09, 127.92, 127.40, 126.28, 126.11, 109.53, 89.54, 75.94, 56.17, 50.41, 48.23, 23.95, 20 .84, 18.13, 15.97. 475

(Thin Film) 3379, 2940, 1769, 1736, 1677, 1598, 1500, 1277, 1192, 1174, 1151, 1033, 953 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₉ H ₃₁ F ₂ N ₂ O ₈ , 573.2043; found 573,2055 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.41 (d, J=4.6 Hz, 1H), 8.31 (d, J=5.4 Hz, 1H), 7.37 (dd, J =8.5, 6.7 Hz, 1H), 7.12 (dd, J=8.3, 6.7 Hz, 1H), 6.99 (d, J=5.5 Hz, 1H), 6 .63-6.44 (m, 4H), 5.86 (dc, J=9.5, 6.2 Hz, 1H), 4.83 (d, J=9.5 Hz, 1H), 4, 62-4.45(m, 1H), 3.90(s, 3H), 3.82(s, 3H), 3.73(s, 3H), 2.38(s, 3H), 1.21 (d, J=6.2 Hz, 3H), 1.01 (d, J=7.2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -113.49, -113.81. 476

(Thin Film) 3382, 3028, 2984, 1736, 1677, 1498, 1451, 1436, 1310, 1201, 1043, 967, 910, 829, 728, 703 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₈ H ₃₁ N ₂ O ₇ , 507.2126; found 507.2141 Mixture of diastereomers 1:1. ¹ H NMR (500 MHz, CDCl ₃ ) δ 8.52-8.46 (m, 1H), 8.20 (d, J=7.6 Hz, 1H), 8.16 (d, J=7, 5 Hz, 1H), 7.33-7.10 (m, 11H), 5.86-5.74 (m, 3H), 4.61-4.48 (m, 1H), 4.10-4 .04 (m, 1H), 4.02 (s, 3H), 2.06 (s, 3H), 2.05 (s, 3H), 1.31 (d, J=7.1 Hz, 3H) , 1.28-1.20 (m, 3H), 0.91 (d, J=7.2 Hz, 3H). 477

(Thin film) 3376, 2985, 2228, 1769, 1738, 1674, 1505 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₉ H ₂₇ N ₄ O ₆ , 527.1925; found 527,1931 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.30 (d, J=5.5 Hz, 1H), 7.60 (d, J=8.3 Hz, 2H), 7.54 (d, J =8.3 Hz, 2H), 7.41-7.30 (m, 4H), 7.03 (d, J=5.5 Hz, 1H), 5.76 (dc, J=8.8, 6.1 Hz, 1H), 4.60-4.52 (m, 1H), 4.20 (d, J=9.0 Hz, 1H), 3.95 (d, J=9.9 Hz, 1H), 3.92 (s, 3H), 2.39 (s, 3H), 1.25 (d, J=6.2 Hz, 3H), 1.08 (d, J=7.2 Hz, 3H) 478

(Thin film) 3387, 2986, 1772, 1739, 1677, 1617, 1509 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₉ H ₂₇ F ₆ N ₂ O ₆ , 613.1768; found 613,178 ¹ H NMR (400 MHz, CDCl ₃ ) 5 8.38 (d, J=7.9 Hz, 1H), 8.32-8.29 (m, 1H), 7.56 (d, J=7, 9 Hz, 2H), 7.52 (d, J=8.5 Hz, 2H), 7.44-7.36 (m, 4H), 7.01 (dd, J=5.5, 3.5 Hz, 1H), 5.88-5.79 (m, 1H), 4.59-4.53 (m, 1H), 4.22 (d, J=9.2 Hz, 1H), 3.90 (s, 3H), 2.38 (s, 3H), 1.28-1.22 (m, 3H), 0.98 (d, J=7.2 Hz, 3H). 479

(Thin film) 3379, 2980, 1772, 1714, 1678, 1508 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₃ H ₃₇ N ₂ O ₁₀ , 621.2443; found 621,2451 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.38 (d, J=8.7 Hz, 1H), 8.32-8.29 (m, 1H), 7.97 (d, J=8, 3 Hz, 2H), 7.93 (d, J=8.2 Hz, 2H), 7.38 (d, J=8.3 Hz, 2H), 7.34 (d, J=8.4 Hz , 2H), 7.00 (d, J=5.5 Hz, 1H), 5.85 (dc, J=9.6, 6.1 Hz, 1H), 4.59-4.50 (m, 1H), 4.38-4.30 (m, 4H), 4.21 (d, J=9.7 Hz, 1H), 3.89 (s, 3H), 2.38 (s, 3H), 1.36 (t, J=7.3 Hz, 6H), 1.25 (d, J=6.3 Hz, 3H), 0.98 (d, J=7.1 Hz, 3H). 480

(Thin Film) 3379, 2983, 1714, 1676, 1607, 1507 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₄ H ₃₉ N ₂ O ₁₁ , 651.2548; found 651,2560 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.28-8.24 (m, 1H), 8.20 (d, J=7.8 Hz, 1H), 8.00-7.92 (m, 4H), 7.42-7.31 (m, 4H), 6.95 (d, J=5.4 Hz, 1H), 5.85 (dp, J=9.4, 7.2, 6, 6 Hz, 1H), 5.73-5.67 (m, 2H), 4.56 (n, J=6.9 Hz, 1H), 4.39-4.28 (m, 4H), 4, 22 (d, J=9.7 Hz, 1H), 3.91 (d, J=1.5 Hz, 3H), 2.06 (s, 3H), 1.37 (t, J=7.2 Hz, 6H), 1.27 (d, J=6.2 Hz, 3H), 0.98 (d, J=7.1 Hz, 3H). 481

(Thin Film) 3379, 2939, 1737, 1677, 1490, 1247, 1202, 1033 HRMS-ESI (m/z) ([M+Na] ⁺ ) calculated for C ₃₀ H ₃₂ Cl ₂ N ₂ NaO ₉ , 657.1377; found 657,1387 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.26 (d, J=5.4 Hz, 1H), 8.22 (d, J=7.9 Hz, 1H), 7.34 (d, J =8.3 Hz, 1H), 7.09 (d, J=8.0 Hz, 1H), 6.94 (d, J=5.4 Hz, 1H), 6.88-6.82 (m , 2H), 6.81 (s, 1H), 6.76 (d, J=2.0 Hz, 1H), 5.86 (dc, J=9.7, 6.2 Hz, 1H), 5 .72 (s, 2H), 4.84 (d, J=9.6 Hz, 1H), 4.57 (n, J=7.2 Hz, 1H), 3.90 (s, 3H), 3 .83 (s, 3H), 3.74 (s, 3H), 2.06 (s, 3H), 1.22 (d, J=6.2 Hz, 3H), 1.04 (d, J= 7.2 Hz, 3H). 482

(Thin Film) 3380, 2981, 1736, 1677, 1597, 1500, 1274, 1202, 1003 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₂ H ₃₇ F ₂ N ₂ O ₉ , 631.2462; found 631,2461 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.25 (t, J=6.6 Hz, 2H), 7.34 (dd, J=8.5, 6.9 Hz, 1H), 7.13 (td, J=1.9, 6.1, 4.7 Hz, 1H), 6.93 (d, J=5.4 Hz, 1H), 6.60-6.36 (m, 4H), 5.90 (dc, J=10.2, 6.2 Hz, 1H), 5.73 (s, 2H), 4.83 (d, J=10.1 Hz, 1H), 4.63-4 .48 (m, 1H), 4.08-3.79 (m, 7H), 2.06 (s, 3H), 1.47 (t, J=6.9 Hz, 3H), 1.40 ( t, J=6.9 Hz, 3H), 1.23 (d, J=6.2 Hz, 3H), 1.04 (d, J=7.2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -113.76, -114.20. 483

(Thin Film) 3378, 2980, 1736, 1677, 1591, 1491, 1247, 1201, 1040 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₂ H ₃₇ Cl ₂ N ₂ O ₉ , 663.1871; found 663,1877 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.29-8.19 (m, 2H), 7.31 (d, J=8.3 Hz, 1H), 7.11 (d, J=8, 2 Hz, 1H), 6.94 (d, J=5.4 Hz, 1H), 6.86-6.73 (m, 3H), 6.72 (d, J=2.0 Hz, 1H) , 5.89 (dc, J=9.9, 6.2 Hz, 1H), 5.73 (s, 2H), 4.83 (d, J=9.8 Hz, 1H), 4.57 ( n, J=7.2 Hz, 1H), 4.05-3.83 (m, 7H), 2.06 (s, 3H), 1.47 (t, J=6.9 Hz, 3H), 1.39 (t, J=6.9 Hz, 3H), 1.23 (d, J=6.1 Hz, 3H), 1.06 (d, J=7.2 Hz, 3H). 484

(Thin Film) 3378, 2978, 1758, 1734, 1676, 1504, 1200, 1043 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₄ H ₄₃ N ₂ O ₉ , 623.2963; found 623,2962 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.29-8.18 (m, 2H), 7.30 (d, J=7.8 Hz, 1H), 7.13 (d, J=7, 7 Hz, 1H), 6.92 (d, J=5.4 Hz, 1H), 6.67-6.57 (m, 3H), 6.54 (s, 1H), 5.93 (dc, J=10.3, 6.1 Hz, 1H), 5.72 (s, 1H), 5.72 (s, 1H), 4.90 (d, J=10.1 Hz, 1H), 4, 55 (n, J=7.1 Hz, 1H), 4.04-3.81 (m, 7H), 2.26 (s, 3H), 2.23 (s, 3H), 2.05 (d , J=1.8 Hz, 3H), 1.47 (t, J=7.0 Hz, 3H), 1.39 (t, J=7.0 Hz, 3H), 1.23 (d, J =6.1 Hz, 3H), 0.99 (d, J=7.2 Hz, 3H). 485

HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₉ H ₃₁ F ₂ N ₂ O ₈ , 573.2051; found 573,2044 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.39 (d, J=6.9 Hz, 1H), 8.29 (d, J=5.4 Hz, 1H), 7.05-6.92 (m, 3H), 6.89 (dd, J=8.1, 2.1 Hz, 1H), 6.82 (dddd, J=15.8, 8.3, 4.0, 2.1 Hz , 3H), 5.72 (dc, J=9.7, 6.1 Hz, 1H), 4.65-4.48 (m, 1H), 3.99 (d, J=9.8 Hz, 1H), 3.88 (s, 3H), 3.85 (s, 6H), 2.38 (s, 3H), 1.24 (d, J=6.1 Hz, 3H), 1.02 ( e, J=7.1 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -137.20, -137.68. 486

HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₁ H ₃₇ N ₂ O ₈ , 565.2542; found 565,2535 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.43 (d, J=7.8 Hz, 1H), 8.28 (d, J=5.4 Hz, 1H), 7.21 (d, J =8.5 Hz, 1H), 7.17-7.09 (m, 1H), 6.96 (d, J=5.5 Hz, 1H), 6.79-6.57 (m, 4H) , 5.63 (dc, J=9.7, 6.1 Hz, 1H), 4.64-4.50 (m, 1H), 4.38 (d, J=9.9 Hz, 1H), 3.86 (s, 3H), 3.73 (s, 3H), 3.71 (s, 3H), 2.38 (s, 3H), 2.35 (s, 3H), 2.31 (s , 3H), 1.29 (d, J=6.1 Hz, 3H), 1.01 (d, J=7.1 Hz, 3H).
¹³ C NMR (101 MHz, CDCl ₃ ) δ 172.25, 168.81, 162.28, 159.43, 157.80, 157.67, 146.63, 141.55, 137.98, 137.71 , 137.44, 131.95, 131.46, 128.85, 128.22, 116.24, 116.03, 111.25, 110.94, 109.75, 74.80, 56.24, 55 .05, 47.92, 46.23, 20.71, 20.36, 20.28, 18.88, 18.08. 487

HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₀ H ₃₃ F ₂ N ₂ O ₉ , 603.2157; found 603.2150 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.26 (d, J=5.4 Hz, 1H), 8.21 (d, J=7.8 Hz, 1H), 7.06 -6.92 (m, 3H), 6.92-6.74 (m, 4H), 5.84-5.61 (m, 3H), 4.56 (n, J=7.3 Hz, 1H), 4, 00 (d, J=9.8 Hz, 1H), 3.91 (s, 3H), 3.86 (s, 6H), 2.06 (s, 3H), 1.25 (d, J=6 .2 Hz, 3H), 1.02 (d, J=7.2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -137.20, -137.72. 488

(Thin film) 3383, 2938, 2837, 1770, 1733, 1677, 1609, 1586, 1505, 1453 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₁ H ₃₇ N ₂ O ₁₀ , 597.2443; found 597.2438 ¹ H NMR (500 MHz, CDCl ₃ ) δ 8.44 (s, 1H), 8.31 (d, J=5.4 Hz, 1H), 7.33 (d, J=8.5 Hz, 1H ), 7.10 (d, J=8.4 Hz, 1H), 6.98 (d, J=5.5 Hz, 1H), 6.42-6.34 (m, 4H), 5.85 (dc, J=9.7, 6.2 Hz, 1H), 4.81 (d, J=9.8 Hz, 1H), 4.59-4.49 (m, 1H), 3.90 ( s, 3H), 3.82 (s, 3H), 3.75 (s, 3H), 3.74 (s, 3H), 3.73 (s, 3H), 2.38 (s, 3H), 1.21 (d, J=6.2 Hz, 3H), 0.99 (d, J=7.2 Hz, 3H). 489

(Thin film) 3382, 2937, 1771, 1733, 1677, 1572, 1505, 1452 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₁ H ₃₇ N ₂ O ₈ , 565.2544; found 565,2541 ¹ H NMR (500 MHz, CDCl ₃ ) δ 8.44 (s, 1H), 8.31 (d, J=5.4 Hz, 1H), 7.31 (d, J=7.7 Hz, 1H ), 7.10 (d, J=8.1 Hz, 1H), 6.98 (d, J=5.5 Hz, 1H), 6.69-6.65 (m, 1H), 6.65 -6.62 (m, 2H), 6.60-6.54 (m, 1H), 5.89 (dc, J=9.8, 6.2 Hz, 1H), 4.90 (d, J =9.8 Hz, 1H), 4.58-4.48 (m, 1H), 3.90 (s, 3H), 3.82 (s, 3H), 3.73 (s, 3H), 2 .38 (s, 3H), 2.27 (s, 3H), 2.25 (s, 3H), 1.21 (d, J=6.2 Hz, 3H), 0.95 (d, J= 7.2 Hz, 3H). 490

(Thin Film) 3383, 2937, 2836, 1772, 1735, 1678, 1502, 1453 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₁ H ₃₇ N ₂ O ₈ , 565.2544; found 565,2538 ¹ H NMR (500 MHz, CDCl ₃ ) δ 8.45 (s, 1H), 8.32 (d, J=5.4 Hz, 1H), 7.22 (d, J=2.1 Hz, 1H ), 7.03 (d, J=2.2 Hz, 1H), 6.98 (d, J=5.5 Hz, 1H), 6.93 (ddd, J=8.3, 2.3, 0.8 Hz, 1H), 6.89 (ddd, J=8.2, 2.2, 0.8 Hz, 1H), 6.73 (d, J=8.3 Hz, 1H), 6, 67 (d, J=8.2 Hz, 1H), 5.85 (dc, J=10.0, 6.2 Hz, 1H), 4.95 (d, J=10.0 Hz, 1H), 4.58-4.46(m, 1H), 3.90(s, 3H), 3.82(s, 3H), 3.72(s, 3H), 2.38(s, 3H), 2 .25 (s, 3H), 2.21 (s, 3H), 1.22 (d, J=6.1 Hz, 3H), 0.95 (d, J=7.1 Hz, 3H). 491

(Thin Film) 3382, 2985, 2941, 2840, 1771, 1736, 1677, 1578, 1508, 1479 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₉ H ₃₁ F ₂ N ₂ O ₈ , 573.2043; found 573,2042 ¹ H NMR (500 MHz, CDCl ₃ ) for both isomers of 1:1 mixture of diastereomers d 8.40 (s, 1H), 8.38 (s, 1H), 8.32 (d, J=5.0 Hz, 1H), 8.31 (d, J=5.3 Hz, 1H), 7.21-7.13 (m, 2H), 7.03-6.83 (m, 12H), 5.76-5 .63 (m, 2H), 5.04 (d, J=11.9 Hz, 1H), 5.02 (d, J=11.2 Hz, 1H), 4.63-4.47 (m, 2H), 3.93 (d, J=2.0 Hz, 3H), 3.92 (s, 3H), 3.91-3.89 (m, 6H), 3.80 (d, J=1 .7 Hz, 3H), 3.76 (d, J=1.6 Hz, 3H), 2.39 (s, 3H), 2.38 (s, 3H), 1.31 (d, J=7 .2 Hz, 3H), 1.29-1.22 (m, 6H), 1.03 (d, J=7.2 Hz, 3H). 492

(Thin film) 3383, 2941, 2839, 1770, 1736, 1677, 1592, 1495 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₉ H ₃₁ F ₂ N ₂ O ₈ , 573.2043; found 573,2045 ¹ H NMR (500 MHz, CDCl ₃ ) for the main isomer of a 2:1 mixture of diastereomers d 8.44 (s, 1H), 8.32 (d, J=5.5 Hz, 1H), 7.18 (dd, J=9.7, 3.0 Hz, 1H), 6.99 (d, J=5.5 Hz, 1H), 6.96 (dd, J=9.5, 3.0 Hz, 1H), 6.87-6.79 (m, 2H), 6.76 (dd, J=9.0, 4.6 Hz, 1H), 6.72 (d, J=4.6 Hz, 1H), 5 .87 (dc, J=9.6, 6.2 Hz, 1H), 4.88 (d, J=9.6 Hz, 1H), 4.60-4.53 (m, 1H), 3, 90 (s, 3H), 3.83 (s, 3H), 3.74 (s, 3H), 2.38 (s, 3H), 1.23 (d, J=6.2 Hz, 3H), 1.02 (d, J=7.2 Hz, 3H). 493

HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₂ H ₃₉ N ₂ O ₁₁ , 627.2548; found 627,2546 ¹ H NMR (500 MHz, CDCl ₃ ) for 1:1 mixture of diastereomers δ 8.26 (t, J=5.1 Hz, 4H), 7.07 (ddd, J=13.9, 7.9, 1 .1 Hz, 2H), 7.00-6.89 (m, 6H), 6.85 (td, J=8.8, 8.0, 1.3 Hz, 2H), 6.78-6, 72 (m, 4H), 5.75-5.71 (m, 4H), 5.71-5.62 (m, 2H), 5.12 (dd, J=13.7, 9.8 Hz, 2H), 4.63-4.47 (m, 2H), 3.91 (s, 3H), 3.90 (s, 3H), 3.89 (s, 3H), 3.86 (s, 3H ), 3.84 (s, 3H), 3.83 (s, 3H), 3.81 (s, 3H), 3.80 (s, 3H), 3.74 (s, 3H), 3.71 (s, 3H), 2.06 (s, 6H), 1.32 (d, J=7.1 Hz, 3H), 1.26 (d, J=6.0 Hz, 3H), 1.24 (d, J=6.2 Hz, 3H), 1.00 (d, J=7.2 Hz, 3H).
¹³ C NMR (126 MHz, CDCl ₃ ) for 1:1 mixture of diastereomers δ 172.36, 171.98, 170.28, 162.82, 162.78, 160.26, 160.23, 152.82, 152 .78, 152.71, 147.42, 147.31, 147.19, 147.11, 145.68, 143.95, 143.93, 142.70, 142.64, 135.14, 134.87 , 134.78, 134.61, 123.66, 123.62, 121.05, 120.97, 120.46, 120.33, 110.74, 110.61, 110.55, 109.44, 99 .98, 89.63, 89.59, 73.81, 73.75, 60.40, 60.36, 60.31, 60.25, 56.17, 56.16, 55.64, 55.59 , 48.18, 48.12, 41.96, 41.83, 29.28, 20.88, 18.86, 18.71, 18.41, 17.91. 494

HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₄ H ₄₃ N ₂ O ₁₁ , 655.2861; found 655,2858 ¹ H NMR (500 MHz, CDCl ₃ ) for 1:1 mixture of diastereomers 5 8.40-8.28 (m, 2H), 8.26 (dd, J=53, 3.7 Hz, 2H), 7, 07 (ddd, J=13.1, 8.0, 1.2 Hz, 2H), 7.03-6.89 (m, 6H), 6.88-6.80 (m, 2H), 6, 75 (td, J=5.6, 2.8 Hz, 4H), 5.81-5.72 (m, 4H), 5.72-5.62 (m, 2H), 5.12 (dd, J=13.4, 9.8 Hz, 2H), 4.54 (dp, J=11.6, 12 Hz, 2H), 3.89 (s, 3H), 3.89 (s, 3H), 3.88 (s, 3H), 3.86 (s, 3H), 3.84 (s, 3H), 3.83 (s, 3H), 3.81 (s, 3H), 3.80 (s , 3H), 3.74 (s, 3H), 3.71 (s, 3H), 2.54 (pd, J=7.0, 4.2 Hz, 2H), 1.32 (d, J= 7.1 Hz, 3H), 1.26 (d, J=6.1 Hz, 3H), 1.24 (d, J=6.2 Hz, 3H), 1.14 (d, J=3, 1 Hz, 6H), 1.13 (d, J=3.1 Hz, 6H), 1.00 (d, J=7.2 Hz, 3H).
¹³ C NMR (126 MHz, CDCl ₃ ) for 1:1 mixture of diastereomers δ 176.26, 176.24, 172.37, 171.99, 162.79, 162.73, 160.25, 160.21, 152 .82, 152.78, 152.70, 147.42, 147.32, 147.19, 147.11, 145.53, 144.22, 144.16, 142.27, 135.14, 134.88 134.79 134.62 123.66 123.62 121.06 120.97 120.47 120.33 110.76 110.74 110.61 110.55 109 .39, 99.98, 90.02, 89.95, 73.79, 73.73, 60.40, 60.36, 60.31, 60.26, 56.12, 56.10, 55.64 , 55.59, 48.18, 48.12, 41.96, 41.82, 33.87, 33.85, 18.85, 18.68, 18.41, 17.91. 495

HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₁ H ₃₇ N ₂ O ₁₀ , 597.2443; found 597.2434 ¹ H NMR (500 MHz, CDCl ₃ ) for 1:1 mixture of diastereomers δ 8.45 (s, 2H), 8.32 (d, J=3.9 Hz, 1H), 8.31 (d, J= 3.9 Hz, 1H), 7.07 (ddd, J=12.2, 8.0, 1.3 Hz, 2H), 7.01-6.89 (m, 6H), 6.89-6 .79 (m, 2H), 6.75 (td, J=6.8, 1.5 Hz, 4H), 5.73-5.60 (m, 2H), 5.12 (d, J=10 .1 Hz, 1H), 5.10 (d, J=9.5 Hz, 1H), 4.61-4.52 (m, 1H), 4.52-4.44 (m, 1H), 3 .91 (s, 3H), 3.90 (s, 3H), 3.89 (s, 3H), 3.86 (s, 3H), 3.83 (s, 3H), 3.83 (s, 3H), 3.81 (s, 3H), 3.80 (s, 3H), 3.73 (s, 3H), 3.72 (s, 3H), 2.39 (s, 3H), 2, 38 (s, 3H), 1.30 (d, J=7.1 Hz, 3H), 1.27-1.22 (m, 6H), 0.98 (d, J=7.1 Hz, 3H ).
¹³ C NMR (126 MHz, CDCl ₃ ) for 1:1 mixture of diastereomers δ 172.26, 171.87, 168.91, 162.22, 162.18, 159.42, 159.39, 152.82, 152 .77, 152.70, 147.40, 147.32, 147.18, 147.11, 146.63, 141.62, 137.45, 137.41, 135.11, 134.85, 134.76 , 134.60, 123.66, 123.64, 121.06, 120.97, 120.48, 120.33, 110.74, 110.61, 110.55, 109.65, 73.83, 73 .78, 60.40, 60.38, 60.31, 60.28, 56.28, 56.26, 55.65, 55.63, 55.58, 48.01, 47.91, 41.81 , 20.76, 18.84, 18.68, 18.48, 18.07. 496

HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₁ H ₃₇ N ₂ O ₈ , 565.2544; found 565,2538 ¹ H NMR (500 MHz, CDCl ₃ ) for 1:1 mixture of diastereomers 8 8.43 (s, 2H), 8.32 (d, J=4.4 Hz, 1H), 8.31 (d, J= 4.4 Hz, 1H), 7.39-7.30 (m, 2H), 7.13 (t, J=9.0 Hz, 2H), 7.05-6.86 (m, 10H), 5.74-5.58 (m, 2H), 5.09 (d, J=9.7 Hz, 1H), 5.06 (d, J=9.1 Hz, 1H), 4.53 (dc , J=15.5, 7.5 Hz, 2H), 3.91 (s, 3H), 3.90 (s, 3H), 3.83 (s, 3H), 3.79 (s, 3H) , 3.70 (s, 3H), 3.68 (s, 3H), 2.39 (s, 3H), 2.38 (s, 3H), 2.30 (s, 3H), 2.29 ( s, 3H), 2.25 (s, 6H), 1.30-1.23 (m, 9H), 0.92 (d, J=7.2 Hz, 3H).
¹³ C NMR (126 MHz, CDCl ₃ ) for 1:1 mixture of diastereomers δ 172.25, 171.70, 168.90, 162.23, 162.17, 159.44, 159.40, 156.93, 156 .89, 156.82, 156.75, 146.64, 146.57, 141.65, 141.59, 137.42, 134.11, 133.96, 133.86, 133.76, 131.20 131.14 131.04 130.95 130.03 129.76 129.70 126.87 126.70 126.65 126.37 123.81 109.65 74 .38, 74.32, 60.31, 60.23, 60.20, 56.29, 56.27, 47.98, 47.84, 41.65, 20.75, 19.06, 18.90 , 18.41, 18.00, 16.68, 16.47. 497

HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₁ H ₃₇ N ₂ O ₈ , 565.2544; found 565,2529 ¹ H NMR (400 MHz, CDCl ₃ ) for 1:1 mixture of diastereomers δ 8.50-8.23 (m, 4H), 7.13-6.92 (m, 8H), 6.86 (t, J =7.1 Hz, 2H), 6.73-6.63 (m, 4H), 5.77-5.58 (m, 2H), 4.61 (t, J=9.4 Hz, 2H) , 4.49 (dp, J=26.5, 7.1 Hz, 2H), 3.90 (s, 3H), 3.89 (s, 3H), 3.79 (s, 3H), 3, 78 (s, 3H), 3.76 (s, 3H), 3.75 (s, 3H), 2.38 (d, J=0.9 Hz, 6H), 2.28 (s, 3H), 2.26 (s, 3H), 2.20 (s, 3H), 2.18 (s, 3H), 1.27 (dt, J=6.4, 3.2 Hz, 9H), 0.96 (d, J=7.1 Hz, 3H).
¹³ C NMR (101 MHz, CDCl ₃ ) for 1:1 mixture of diastereomers δ 172.28, 171.77, 168.85, 162.24, 159.41, 157.72, 157.55, 146.61, 141 .63, 140.75, 140.51, 140.12, 137.47, 126.12, 126.08, 125.91, 125.42, 120.51, 120.39, 119.92, 119.76 , 109.64, 108.32, 74.77, 74.71, 56.26, 55.45, 53.40, 48.08, 47.90, 47.55, 20.72, 18.81, 18 .67, 18.29, 17.98, 11.80, 11.73, 11.43. 498

(Thin Film) 3384, 2942, 1771, 1737, 1677, 1501, 1475, 1430, 1308, 1200, 1175, 1100, 1057, 950, 908, 731 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₉ H ₂₉ F ₄ N ₂ O ₈ , 609.1855; found 609,1851 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.35 (d, J=5.5 Hz, 1H), 8.30 (d, J=5.4 Hz, 1H), 7.07 (ddd, J =8.2, 5.7, 2.2 Hz, 1H), 7.00 (d, J=5.5 Hz, 1H), 6.86-6.72 (m, 3H), 5.70- 5.62(m, 1H), 4.85(d, J=9.4Hz, 1H), 4.62-4.54(m, 1H), 3.97(d, J=2.3Hz , 3H), 3.91 (s, 3H), 3.83 (d, J=2.0 Hz, 3H), 2.38 (s, 3H), 1.23 (d, J=6.1 Hz , 3H), 1.11 (d, J=7.2 Hz, 3H).
¹³ C NMR (126 MHz, CDCl ₃ ) δ 172.04, 168.90, 162.27, 159.48, 149.41, 147.34-146.78 (m), 146.60, 143.34, 141.37, 137.50, 129.96-129.37 (m), 123.61-122.42 (m), 110.81 (d, J=13.5 Hz), 110.68 (d, J=13.2 Hz), 109.78, 72.31, 61.44-60.78 (m), 56.31, 47.89, 42.40, 20.74, 18.77, 18.11 . 499

(Thin Film) 3381, 2938, 1771, 1734, 1677, 1504, 1451, 1310, 1198, 1175, 1147, 1043, 908, 806, 730 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₁ H ₃₇ N ₂ O ₆ , 533.2646; found 533.2651 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.43 (s, 1H), 8.32 (d, J=5.4 Hz, 1H), 7.11-6.83 (m, 7H), 5 .66 (dc, J=10.0, 6.1 Hz, 1H), 4.57-4.48 (m, 1H), 4.45 (d, J=10.0 Hz, 1H), 3, 90 (s, 3H), 2.38 (s, 3H), 2.35 (s, 3H), 2.29 (s, 3H), 2.27 (s, 3H), 2.25 (s, 3H ), 1.28 (d, J=6.2 Hz, 3H), 0.94 (d, J=7.2 Hz, 3H).
¹³ C NMR (126 MHz, CDCl ₃ ) δ 172.41, 168.91, 162.25, 159.41, 146.64, 141.58, 139.12, 138.59, 137.44, 135.40 , 135.07, 133.59, 133.35, 130.56, 130.27, 128.60, 127.91, 127.20, 126.91, 109.68, 74.87, 56.27, 47 .90, 47.34, 21.28, 21.22, 20.75, 19.79, 19.73, 18.86, 17.98. 500

(Thin Film) 3384, 2938, 1771, 1735, 1677, 1505, 1451, 1309, 1198, 1174, 1100, 1043, 908, 804, 730 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₁ H ₃₇ N ₂ O ₆ , 533.2646; found 533,2642 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.42 (s, 1H), 8.31 (d, J=5.5 Hz, 1H), 7.18 (d, J=7.9 Hz, 1H ), 7.12 (d, J=8.6 Hz, 1H), 6.98 (d, J=5.5 Hz, 1H), 6.96-6.85 (m, 4H), 5.66 (dc, J=9.9, 6.2 Hz, 1H), 4.57-4.48 (m, 1H), 4.43 (d, J=10.0 Hz, 1H), 3.90 ( s, 3H), 2.38 (s, 3H), 2.34 (s, 3H), 2.30 (s, 3H), 2.25 (s, 3H), 2.21 (s, 3H), 1.28 (d, J=6.1 Hz, 3H), 0.96 (d, J=7.1 Hz, 3H).
¹³ C NMR (126 MHz, CDCl ₃ ) δ 172.30, 168.92, 162.24, 159.41, 146.64, 141.59, 137.43, 136.50, 136.40, 136.19 136.10, 135.84, 135.52, 131.49, 131.15, 127.76, 127.14, 126.81, 126.59, 109.67, 74.83, 56.27, 47 .89, 46.82, 20.84, 20.81, 20.76, 20.13, 20.07, 18.92, 18.03. 501

(Thin Film) 3379, 2983, 1770, 1738, 1677, 1496, 1453, 1310, 1199, 1176, 1148, 1043, 909, 808, 729 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₉ H ₃₁ F ₂ N ₂ O ₆ , 541.2145; found 541,2146 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.43 (d, J=7.9 Hz, 1H), 8.32 (d, J=5.4 Hz, 1H), 7.13-6.98 (m, 4H), 6.91 (dd, J=10.3, 2.8 Hz, 1H), 6.81 (dtd, J=12.5, 8.2, 2.7 Hz, 2H), 5.57 (dc, J=9.6, 6.1 Hz, 1H), 4.61-4.51 (m, 1H), 4.46 (d, J=9.6 Hz, 1H), 3 .90 (s, 3H), 2.38 (s, 3H), 2.34 (s, 3H), 2.29 (s, 3H), 1.32 (d, J=6.2 Hz, 3H) , 1.02 (d, J=7.2 Hz, 3H).
¹³ C NMR (126 MHz, CDCl ₃ ) δ 172.15, 168.90, 162.31, 161.35 (d, J=243.7 Hz), 159.42, 146.68, 141.44, 140 .63 (d, J=6.5 Hz), 140.14 (d, J=6.7 Hz), 137.47, 132.40 (d, J=3.1 Hz), 132.06 (d , J=2.0 Hz), 132.01 (d, J=3.1 Hz), 131.69 (d, J=7.8 Hz), 114.83 (d, J=22.2 Hz) , 114.37 (d, J=22.3 Hz), 113.65 (d, J=20.8 Hz), 113.37 (d, J=20.6 Hz), 109.75, 74.02 , 56.28, 47.77, 47.72, 20.75, 19.42, 19.35, 18.83, 18.00. 502

(Thin Film) 3378, 2940, 1770, 1738, 1677, 1498, 1207, 1176, 1151, 1037, 816, 730 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₉ H ₃₁ F ₂ N ₂ O ₈ , 573.2043; found 573,2047 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.42 (d, J=7.6 Hz, 1H), 8.32 (d, J=5.4 Hz, 1H), 7.01-6.97 (m, 1H), 6.96-6.91 (m, 2H), 6.88 (d, J=9.3 Hz, 1H), 6.86-6.81 (m, 1H), 6, 70 (dt, J=9.0, 3.5 Hz, 1H), 6.65 (dt, J=9.0, 3.5 Hz, 1H), 5.83 (dc, J=12.0, 6.1 Hz, 1H), 4.69 (d, J=10.3 Hz, 1H), 4.57 (p, J=7.3 Hz, 1H), 3.90 (s, 3H), 3 .74 (s, 6H), 2.38 (s, 3H), 1.30 (d, J=6.2 Hz, 3H), 1.02 (d, J=7.1 Hz, 3H).
¹³ C NMR (126 MHz, CDCl ₃ ) δ 172.11, 168.90, 162.25, 159.42, 155.73 (d, J=1.8 Hz), 155.57 (d, J=2 .0 Hz), 155.19 (d, J=238.6 Hz), 154.96 (d, J=238.7 Hz), 146.63, 141.51, 137.44, 127.90 (d , J=15.8 Hz), 127.66 (d, J=16.2 Hz), 116.23 (d, J=24.8 Hz), 115.96 (d, J=24.9 Hz) , 115.16, 114.23, 113.21-112.82 (m), 109.69, 72.01, 56.28, 55.71, 47.85, 43.39, 20.75, 18, 96, 18.05. 503

(Thin Film) 3379, 2938, 1770, 1736, 1676, 1623, 1585, 1506, 1444, 1310, 1195, 1175, 1154, 1031, 907, 832, 803, 729 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₉ H ₃₁ F ₂ N ₂ O ₈ , 573.2043; found 573,2044 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.42 (s, 1H), 8.32 (d, J=5.4 Hz, 1H), 7.29 (t, J=8.7 Hz, 1H ), 7.16 (t, J=8.5 Hz, 1H), 6.99 (d, J=5.5 Hz, 1H), 6.65-6.55 (m, 3H), 6.51 (dd, J=12.0, 2.6 Hz, 1H), 5.78 (dc, J=12.1, 6.2 Hz, 1H), 4.66-4.52 (m, 2H), 3.90 (s, 3H), 3.75 (s, 3H), 3.72 (s, 3H), 2.38 (s, 3H), 1.27 (d, J=6.2 Hz, 3H ), 1.06 (d, J=7.2 Hz, 3H).
¹³ C NMR (126 MHz, CDCl ₃ ) δ 172.11, 168.91, 162.24, 161.24 (d, J=245.7 Hz), 161.01 (d, J=245.9 Hz) , 159.72 (d, J=11.2 Hz), 159.46 (d, J=11.3 Hz), 159.44, 146.60, 141.51, 137.44, 129.90 (d , J=5.4 Hz), 129.34 (d, J=5.6 Hz), 119.60 (d, J=14.6 Hz), 119.45 (d, J=15.0 Hz) , 110.13 (d, J=3.0 Hz), 109.85-109.61 (m), 101.99-101.44 (m), 72.26, 56.28, 55.50, 55 .46, 47.88, 41.64, 20.75, 18.93, 18.13. 504

(Thin Film) 3381, 2942, 1772, 1728, 1679, 1508, 1456, 1417, 1327, 1242, 1172, 1121, 1033, 904, 739 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₁ H ₃₁ F ₆ N ₂ O ₈ , 673.1979; found 673,1985 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.40 (s, 1H), 8.31 (d, J=5.4 Hz, 1H), 7.54 (d, J=8.0 Hz, 1H ), 7.30 (d, J=7.8 Hz, 1H), 7.12 (d, J=8.0 Hz, 2H), 7.04-6.97 (m, 3H), 6.01 -5.91(m, 1H), 4.99(d, J=9.3Hz, 1H), 4.60-4.46(m, 1H), 3.90(s, 3H), 3, 89 (s, 3H), 3.81 (s, 3H), 2.38 (s, 3H), 1.24 (d, J=6.2 Hz, 3H), 0.98 (d, J=7 .2 Hz, 3H).
¹³ C NMR (126 MHz, CDCl ₃ ) δ 172.17, 162.27, 159.47, 157.54, 157.39, 146.61, 141.44, 137.49, 132.44, 130.44 -129.46 (m), 117.00, 109.74, 107.51 (d, J=25.6 Hz), 99.99, 71.95, 56.28, 55.73, 55.69, 47.82, 43.70, 20.73, 18.89, 17.97. 505

(Thin Film) 3375, 2939, 1770, 1677, 1592, 1509, 1195, 1136, 1059, 731 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₉ H ₃₁ F ₂ N ₂ O ₈ , 573.2043; found 573,2034 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.42 (d, J=7.9 Hz, 1H), 8.32 (d, J=5.5 Hz, 1H), 6.99 (d, J =5.5 Hz, 1H), 6.66-6.53 (m, 4H), 6.45 (ddt, J=14.8, 10.5, 2.3 Hz, 2H), 5.67 ( dk, J=9.9, 6.1 Hz, 1H), 4.62-4.49 (m, 1H), 3.94 (d, J=9.9 Hz, 1H), 3.90 (s , 3H), 3.76 (s, 3H), 3.75 (s, 3H), 2.38 (s, 3H), 1.25 (d, J=7.6 Hz, 3H), 1.02 (d, J=7.2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -110.67, -111.17. 506

(Thin Film) 3375, 2938, 1770, 1677, 1593, 1203, 1152, 1064, 731 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₁ H ₃₇ N ₂ O ₁₀ , 597.2443; found 597,2442 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.42 (d, J=7.7 Hz, 1H), 8.32 (d, J=5.4 Hz, 1H), 6.98 (d, J =5.5Hz, 1H), 6.45 (dd, J=6.5, 2.3Hz, 4H), 6.28 (dt, J=MA, 2.3Hz, 2H), 5.74 (dc, J=10.3, 6.1 Hz, 1H), 4.59-4.48 (m, 1H), 3.93-3.86 (m, 4H), 3.76 (s, 6H ), 3.74 (s, 6H), 2.38 (s, 3H), 1.28-1.22 (m, 3H), 0.97 (d, J=7.2 Hz, 3H).
¹³ C NMR (101 MHz, CDCl ₃ ) δ 172.26, 168.86, 162.29, 160.95, 160.78, 159.43, 146.64, 143.47, 143.25, 141.64 , 137.47, 109.69, 106.48, 106.26, 98.54, 98.44, 72.91, 58.21, 56.26, 55.30, 55.28, 47.92, 20 .73, 19.23, 18.01. 507

(Thin Film) 3384, 2939, 1771, 1677, 1593, 1508, 1172, 1152, 1066, 732 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₁ H ₃₇ N ₂ O ₈ , 565.2544; found 565,2540 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.42 (d, J=7.9 Hz, 1H), 8.32 (d, J=5.4 Hz, 1H), 6.98 (d, J =5.5 Hz, 1H), 6.69 (d, J=1.5 Hz, 2H), 6.64 (dt, J=4.2, 1.9 Hz, 2H), 6.54 (t , J=1.9 Hz, 1H), 6.49 (t, J=1.9 Hz, 1H), 5.73 (dc, J=10.3, 6.1 Hz, 1H), 4.59 -4.47 (m, 1H), 3.89 (s, 4H), 3.75 (s, 3H), 3.73 (s, 3H), 2.38 (s, 3H), 2.28 ( s, 3H), 2.25 (s, 3H), 1.23 (d, J=6.1 Hz, 3H), 0.93 (d, J=7.1 Hz, 3H).
¹³ C NMR (101 MHz, CDCl ₃ ) δ 172.30, 168.86, 162.27, 159.77, 159.64, 159.43, 146.64, 142.75, 142.51, 141.67 , 139.73, 139.31, 137.46, 121.35, 121.29, 112.68, 111.36, 110.95, 109.68, 73.23, 57.88, 56.26, 55 .15, 55.13, 47.91, 29.30, 21.67, 21.60, 20.73, 19.27, 17.96. 508

(Thin Film) 3376, 2939, 1771, 1678, 1508, 1201, 1040, 734 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₁ H ₃₇ N ₂ O ₈ , 565.2544; found 565,2538 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.40 (d, J=7.9 Hz, 1H), 8.31 (d, J=5.4 Hz, 1H), 7.06-6.94 (m, 3H), 6.80 (ddd, J=7.7, 6.1, 1.7 Hz, 2H), 6.73 (dd, J=14.2, 1.6 Hz, 2H), 5.79 (dc, J=10.1, 6.1 Hz, 1H), 4.60-4.47 (m, 1H), 3.96 (d, J=10.1 Hz, 1H), 3 .89 (s, 3H), 3.79 (s, 3H), 3.79 (s, 3H), 2.38 (s, 3H), 2.14 (s, 3H), 2.11 (s, 3H), 1.24 (d, J=6.4 Hz, 3H), 0.93 (d, J=7.2 Hz, 3H).
¹³ C NMR (101 MHz, CDCl ₃ ) δ 172.31, 168.86, 162.28, 159.44, 157.84, 157.65, 146.62, 141.65, 140.39, 140.28 , 137.48, 130.75, 130.48, 125.19, 124.79, 119.76, 119.68, 109.94, 109.85, 109.69, 73.32, 57.89, 56 .26, 55.29, 47.93, 29.30, 20.73, 19.30, 17.97, 15.80, 15.75. 509

(Thin Film) 3373, 2939, 1770, 1676, 1513, 1276, 1201, 1026, 731 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₉ H ₃₁ F ₂ N ₂ O ₈ , 573.2043; found 573,2033 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.40 (d, J=7.9 Hz, 1H), 8.32 (d, J=5.4 Hz, 1H), 7.04-6.91 (m, 5H), 6.86 (dt, J=11.1, 8.7 Hz, 2H), 5.63 (dc, J=9.4, 6.1 Hz, 1H), 4.64- 4.51 (m, 1H), 3.92 (d, J=9.5 Hz, 1H), 3.90 (s, 3H), 3.84 (s, 3H), 3.82 (s, 3H ), 2.38 (s, 3H), 1.22 (d, J=6.2 Hz, 3H), 1.05 (d, J=7.2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -134.20, -134.64. 510

(Thin Film) 3386, 2939, 1771, 1677, 1504, 1201, 1176, 732 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₁ H ₃₇ N ₂ O ₈ , 565.2544; found 565,2526 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.43 (s, 1H), 8.31 (d, J=5.5 Hz, 1H), 7.12-6.94 (m, 5H), 6 .70 (dd, J=14.1, 8.4 Hz, 2H), 5.69 (dc, J=9.9, 6.1 Hz, 1H), 4.60-4.49 (m, 1H ), 3.89 (s, 3H), 3.87 (d, J=10.6 Hz, 1H), 3.77 (s, 3H), 3.74 (s, 3H), 2.38 (s , 3H), 2.16 (s, 3H), 2.14 (s, 3H), 1.21 (d, J=6.1 Hz, 3H), 0.95 (d, J=7.1 Hz , 3H).
¹³ C NMR (101 MHz, CDCl ₃ ) δ 172.30, 168.86, 162.26, 159.43, 156.52, 156.35, 146.63, 141.69, 137.46, 133.70 133.57, 130.50, 130.37, 126.79, 126.37, 126.10, 125.87, 110.05, 109.92, 109.67, 73.70, 56.26, 56 .23, 55.31, 55.29, 47.94, 20.73, 19.29, 18.08, 16.32, 16.25. 511

(Thin Film) 3387, 2940, 1771, 1678, 1499, 1223, 1046, 808, 732 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₁ H ₃₇ N ₂ O ₁₀ , 597.2443; found 597,2410 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.50-8.35 (m, 1H), 8.31 (d, J=5.4 Hz, 1H), 7.07 (d, J=3, 0 Hz, 1H), 6.97 (d, J=5.5 Hz, 1H), 6.87 (d, J=3.0 Hz, 1H), 6.80-6.60 (m, 4H) , 5.91 (dc, J=9.9, 6.1 Hz, 1H), 4.93 (d, J=10.0 Hz, 1H), 4.62-4.45 (m, 1H), 3.89 (s, 3H), 3.81 (s, 3H), 3.74 (s, 3H), 3.71 (s, 3H), 3.70 (s, 3H), 2.38 (s , 3H), 1.23 (d, J=6.1 Hz, 3H), 0.97 (d, J=7.1 Hz, 3H).
¹³ C NMR (101 MHz, CDCl ₃ ) δ 172.29, 168.87, 162.24, 159.40, 153.47, 153.45, 151.89, 151.77, 146.63, 141.73 , 137.43, 130.69, 116.44, 115.43, 112.14, 112.11, 111.84, 111.55, 109.63, 73.04, 56.33, 56.29, 56 .25, 55.68, 55.59, 47.96, 43.90, 29.30, 20.73, 18.91, 18.13. 512

(Thin Film) 3381, 2939, 1771, 1677, 1502, 1200, 1175, 1043, 731 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₁ H ₃₇ N ₂ O ₈ , 565.2544; found 565,2543 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.43 (d, J=8.0 Hz, 1H), 8.31 (d, J=5.4 Hz, 1H), 7.05 (d, J =8.3Hz, 1H), 7.01-6.94(m, 2H), 6.90(d, J=2.7Hz, 1H), 6.82(d, J=2.7Hz , 1H), 6.63 (ddd, J=18.7, 8.4, 2.7 Hz, 2H), 5.65 (dc, J=10.1, 6.1 Hz, 1H), 4, 59-4.49 (m, 1H), 4.45 (d, J=10.0 Hz, 1H), 3.89 (s, 3H), 3.73 (s, 3H), 3.73 (s , 3H), 2.38 (s, 3H), 2.32 (s, 3H), 2.27 (s, 3H), 1.31 (d, J=6.1 Hz, 3H), 0.97 (d, J=7.1 Hz, 3H).
¹³ C NMR (101 MHz, CDCl ₃ ) δ 172.26, 168.85, 162.28, 159.43, 157.92, 157.89, 146.64, 141.63, 140.31, 139.86 137.47, 131.43, 131.10, 128.88, 128.61, 114.65, 113.69, 111.27, 111.11, 109.70, 74.59, 56.26, 55 .19, 47.90, 47.86, 29.30, 20.73, 19.29, 19.25, 18.90, 17.99. 513

(Thin Film) 3381, 2940, 1740, 1675, 1592, 1505, 1200, 1134, 1045, 829, 730 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₀ H ₃₃ F ₂ N ₂ O ₉ , 603.2149; found 603,2137 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.27 (d, J=5.4 Hz, 1H), 8.23 (d, J=7.8 Hz, 1H), 6.94 (d, J =5.4 Hz, 1H), 6.60 (dddd, J=13.2, 10.8, 3.9, 1.8 Hz, 4H), 6.45 (ddt, J=13.9, 10 .5, 2.3 Hz, 2H), 5.76-5.63 (m, 3H), 4.57 (p, J=7.3 Hz, 1H), 3.95 (d, J=10, 0 Hz, 1H), 3.90 (s, 3H), 3.77 (s, 3H), 3.75 (s, 3H), 2.06 (s, 3H), 1.26 (d, J= 6.1 Hz, 3H), 1.04 (d, J=7.2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -110.67, -111.20. 514

(Thin Film) 3382, 2937, 1737, 1675, 1593, 1457, 1202, 1150, 1062, 829, 729 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₂ H ₃₉ N ₂ O ₁₁ , 627.2548; found 627,2555 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.26 (d, J=5.4 Hz, 1H), 8.23 (d, J=7.8 Hz, 1H), 6.93 (d, J =5.4 Hz, 1H), 6.46 (dd, J=7.4, 2.2 Hz, 4H), 6.28 (dt, J=16.6, 2.2 Hz, 2H), 5 .81-5.68 (m, 3H), 4.55 (n, J=7.2 Hz, 1H), 3.96-3.86 (m, 4H), 3.76 (s, 6H), 3.74 (s, 6H), 2.06 (s, 3H), 1.26 (d, J=6.2 Hz, 3H), 0.99 (d, J=7.2 Hz, 3H).
¹³ C NMR (101 MHz, CDCl ₃ ) δ 172.37, 170.22, 162.89, 160.96, 160.79, 160.25, 145.70, 143.93, 143.51, 143.26 , 142.65, 109.51, 106.49, 106.24, 98.54, 98.43, 89.57, 72.87, 58.24, 56.17, 55.30, 55.28, 48 .14, 20.85, 19.25, 17.84. 515

(Thin Film) 3382, 2937, 1738, 1676, 1594, 1504, 1293, 1202, 1152 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₂ H ₃₉ N ₂ O ₉ , 595.2650; found 595,2647 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.27 (d, J=5.4 Hz, 1H), 8.23 (d, J=7.8 Hz, 1H), 6.93 (d, J =5.4Hz, 1H), 6.70(s, 2H), 6.65(dt, J=5.7, 1.9Hz, 2H), 6.55(t, J=1.7Hz , 1H), 6.50 (t, J=1.7 Hz, 1H), 5.80-5.66 (m, 3H), 4.54 (n, J=7.2 Hz, 1H), 3 .93-3.87 (m, 4H), 3.75 (d, J=7.3 Hz, 6H), 2.29 (s, 3H), 2.25 (s, 3H), 2.06 ( s, 3H), 1.24 (d, J=6.1 Hz, 3H), 0.95 (d, J=7.1 Hz, 3H).
¹³ C NMR (101 MHz, CDCl ₃ ) δ 172.41, 170.22, 162.88, 160.25, 159.77, 159.65, 145.70, 143.93, 142.79, 142.70 , 142.52, 139.73, 139.31, 121.35, 121.30, 112.69, 111.36, 110.92, 109.50, 89.57, 73.19, 57.91, 56 .16, 55.15, 55.14, 48.13, 29.30, 21.67, 21.60, 20.85, 19.29, 17.79. 516

(Thin Film) 3382, 2936, 1737, 1676, 1505, 1202, 1040, 969, 730 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₂ H ₃₉ N ₂ O ₉ , 595.2650; found 595,2639 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.26 (d, J=5.4 Hz, 1H), 8.21 (d, J=7.8 Hz, 1H), 7.05-6.96 (m, 2H), 6.93 (d, J=5.4 Hz, 1H), 6.81 (td, J=7.4, 1.6 Hz, 2H), 6.76 (d, J= 1.6 Hz, 1H), 6.72 (d, J=1.6 Hz, 1H), 5.79 (dc, J=10.1, 6.2 Hz, 1H), 5.72 (d, J=1.4Hz, 2H), 4.55(n, J=7.2Hz, 1H), 3.97(d, J=10.2Hz, 1H), 3.90(s, 3H) , 3.80 (s, 3H), 3.79 (s, 3H), 2.14 (s, 3H), 2.11 (s, 3H), 2.06 (s, 3H), 1.26 ( d, J=6.2 Hz, 3H), 0.94 (d, J=7.2 Hz, 3H).
¹³ C NMR (101 MHz, CDCl ₃ ) δ 172.43, 170.21, 162.89, 160.26, 157.85, 157.65, 145.68, 143.94, 142.67, 140.44 , 140.28, 130.75, 130.48, 125.19, 124.78, 119.75, 119.67, 109.94, 109.86, 109.52, 89.56, 73.28, 57 .91, 56.17, 55.29, 55.28, 48.16, 20.85, 19.32, 17.82, 15.80, 15.75. 517

(Thin Film) 3382, 2984, 1739, 1675, 1512, 1275, 1202, 730 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₀ H ₃₃ F ₂ N ₂ O ₉ , 603.2149; found 603,2137 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.27 (d, J=5.4 Hz, 1H), 8.23 (d, J=7.9 Hz, 1H), 7.04-6.92 (m, 5H), 6.87 (q, J=8.7 Hz, 2H), 5.72 (s, 2H), 5.64 (dc, J=9.5, 6.2 Hz, 1H) , 4.65-4.48 (m, 1H), 3.93 (d, J=9.7 Hz, 1H), 3.91 (s, 3H), 3.84 (s, 3H), 3. 83 (s, 3H), 2.06 (s, 3H), 1.24 (d, J=6.1 Hz, 3H), 1.06 (d, J=7.2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -134.20, -134.65. 518

(Thin film) 3382, 2941, 1737, 1676, 1503, 1248, 1203, 730 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₂ H ₃₉ N ₂ O ₉ , 595.2650; found 595,2645 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.27 (s, 1H), 8.23 (d, J=7.9 Hz, 1H), 7.11-6.99 (m, 5H), 6 .93 (d, J=5.3 Hz, 1H), 6.71 (dd, J=12.0, 8.4 Hz, 2H), 5.74-5.65 (m, 3H), 4, 55 (n, J=7.2 Hz, 1H), 3.90 (s, 3H), 3.77 (s, 3H), 3.75 (s, 3H), 2.16 (s, 3H), 2.14 (s, 3H), 2.06 (s, 3H), 1.23 (d, J=6.2 Hz, 3H), 0.97 (d, J=7.2 Hz, 3H).
¹³ C NMR (101 MHz, CDCl ₃ ) δ 172.43, 170.22, 162.87, 160.26, 156.53, 156.36, 145.68, 143.94, 142.72, 133.75 , 133.58, 130.48, 130.36, 126.81, 126.38, 126.10, 125.87, 110.06, 109.93, 109.49, 89.58, 73.66, 56 .27, 56.16, 55.33, 55.30, 48.16, 20.85, 19.32, 17.91, 16.33, 16.25. 519

(Thin Film) 3381, 2939, 1737, 1676, 1498, 1233, 1043, 729 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₂ H ₃₉ N ₂ O ₁₁ , 627.2548; found 627,2541 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.25 (dd, J=6.5, 3.4 Hz, 2H), 7.07 (d, J=3.0 Hz, 1H), 6.92 (d, J=5.4 Hz, 1H), 6.87 (d, J=3.1 Hz, 1H), 6.77 (d, J=8.8 Hz, 1H), 6.71 (d , J=8.8 Hz, 1H), 6.66 (ddd, J=11.1, 8.9, 3.0 Hz, 2H), 5.92 (dc, J=9.9, 6.1 Hz, 1H), 5.72 (d, J=1.7 Hz, 2H), 4.94 (d, J=10.0 Hz, 1H), 4.56 (n, J=7.2 Hz, 1H), 3.89 (s, 3H), 3.81 (s, 3H), 3.74 (s, 3H), 3.72 (s, 3H), 3.71 (s, 3H), 2, 06 (s, 3H), 1.25 (d, J=6.3 Hz, 3H), 0.99 (d, J=7.2 Hz, 3H).
¹³ C NMR (101 MHz, CDCl ₃ ) δ 172.39, 170.22, 162.84, 160.23, 153.47, 153.45, 151.89, 151.78, 145.68, 143.88 , 142.78, 130.73, 130.69, 116.45, 115.38, 112.14, 112.13, 111.83, 111.55, 109.45, 89.59, 73.02, 56 .34, 56.29, 56.15, 55.67, 55.59, 48.17, 43.90, 20.86, 18.91, 17.97. 520

(Thin Film) 3382, 2937, 1739, 1677, 1500, 1455, 1202, 1042, 730 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₂ H ₃₉ N ₂ O ₉ , 595.2650; found 595,2652 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.26 (d, J=5.4 Hz, 1H), 8.23 (d, J=7.8 Hz, 1H), 7.05 (d, J =8.5 Hz, 1H), 6.98 (d, J=8.4 Hz, 1H), 6.93 (d, J=5.4 Hz, 1H), 6.90 (d, J=2 .1 Hz, 1H), 6.82 (d, J=2.7 Hz, 1H), 6.63 (ddd, J=18.1, 8.3, 2.7 Hz, 2H), 5.72 (d, J=1.6 Hz, 2H), 5.66 (dc, J=10.0, 6.1 Hz, 1H), 4.56 (p, J=13 Hz, 1H), 4.46 (d, J=10.1 Hz, 1H), 3.90 (s, 3H), 3.73 (s, 6H), 2.33 (s, 3H), 2.28 (s, 3H), 2 .06 (s, 3H), 1.32 (d, J=6.1 Hz, 3H), 0.99 (d, J=1.2 Hz, 3H).
¹³ C NMR (101 MHz, CDCl ₃ ) δ 172.37, 170.22, 162.89, 160.25, 157.92, 157.89, 145.69, 143.92, 142.66, 140.37 139.85, 131.44, 131.11, 128.89, 128.62, 114.67, 113.64, 111.28, 111.11, 109.52, 89.57, 74.55, 56 .17, 55.19, 48.13, 47.87, 29.30, 20.86, 19.30, 19.26, 18.88, 17.81. 521

(Thin Film) 3380, 2933, 1769, 1737, 1677, 1496, 1195, 1174, 1095 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₁ H ₃₅ F ₂ N ₂ O ₈ , 602.2389; found 602.2395 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.39 (d, J=7.1 Hz, 1H), 8.31 (d, J=5.4 Hz, 1H), 7.44 (dd, J =8.7, 5.6 Hz, 1H), 7.23 (dd, J=8.7, 5.6 Hz, 1H), 7.11 (dd, J=9.6, 2.8 Hz, 1H), 7.07 (dd, J=9.7, 2.8 Hz, 1H), 7.00 (d, J=5.5 Hz, 1H), 6.96-6.87 (m, 2H ), 5.60 (dc, J=8.5, 6.2 Hz, 1H), 4.69 (d, J=8.8 Hz, 1H), 4.62 (d, J=12.4 Hz , 1H), 4.60-4.53 (m, 1H), 4.50 (d, J=12.6 Hz, 1H), 4.44 (d, J=12.5 Hz, 1H), 4 .40 (d, J=12.5 Hz, 1H), 3.90 (s, 3H), 3.43 (s, 3H), 3.38 (s, 3H), 2.39 (s, 3H) , 1.28 (d, J=6.2 Hz, 3H), 1.04 (d, J=7.2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -115.57, -115.90. 522

(Thin Film) 3385, 2976, 1770, 1738, 1678, 1506, 1200, 1175, 1155, 1096 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₃₃ H ₃₉ F ₂ N ₂ O ₈ , 629.2669; found 629,2666 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.40 (d, J=6.4 Hz, 1H), 8.31 (d, J=5.4 Hz, 1H), 7.45 (dd, J =8.7, 5.6 Hz, 1H), 7.21 (dd, J=8.7, 5.6 Hz, 1H), 7.17-7.05 (m, 2H), 7.00 ( d, J=5.5 Hz, 1H), 6.97-6.82 (m, 2H), 5.62 (dc, J=8.2, 6.2 Hz, 1H), 4.70 (d , J=8.7 Hz, 1H), 4.67 (d, J=12.7 Hz, 1H), 4.62-4.50 (m, 2H), 4.48 (d, J=12, 5 Hz, 1H), 4.43 (d, J=12.7'Hz, 1H), 3.90 (s, 3H), 3.62-3.45 (m, 4H), 2.39 (s , 3H), 1.30-1.25 (m, 6H), 1.23 (t, J=7.0 Hz, 3H), 1.05 (d, J=12 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -115.69, -115.98. 523

HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₈ H ₃₀ FN ₂ O ₇ , 525.2037; found 525,2025 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.41 (d, J=6.8 Hz, 1H), 8.30 (d, J=5.4 Hz, 1H), 7.36-7.28 (m, 2H), 7.26-7.18 (m, 2H), 7.18-7.10 (m, 2H), 6.97 (d, J=5.5 Hz, 1H), 6, 67-6.46 (m, 2H), 5.83 (dc, J=9.9, 6.2 Hz, 1H), 4.62-4.46 (m, 2H), 3.87 (s, 3H), 3.82 (s, 3H), 2.38 (s, 3H), 1.23 (d, J=6.2 Hz, 3H), 0.91 (d, J=7.1 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -113.24. 524

HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₈ H ₃₀ FN ₂ O ₆ , 509.2088; found 509,2083 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.40 (d, J=7.9 Hz, 1H), 8.30 (d, J=5.4 Hz, 1H), 7.35-7.17 (m, 5H), 7.17-7.08 (m, 1H), 6.97 (d, J=5.5 Hz, 1H), 6.93-6.79 (m, 2H), 5, 77 (dc, J=10.2, 6.1 Hz, 1H), 4.60-4.47 (m, 1H), 4.28 (d, J=10.2 Hz, 1H), 3.87 (s, 3H), 2.38 (s, 6H), 1.26 (d, J=6.1 Hz, 3H), 0.93 (d, J=7.2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -116.66. 525

HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₈ H ₃₀ FN ₂ O ₇ , 525.2037; found 525,2035 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.42 (d, J=8.1 Hz, 1H), 8.30 (d, J=5.6 Hz, 1H), 7.35-7.21 (m, 5H), 7.17 (ddt, J=6.5, 5.4, 1.8 Hz, 1H), 6.98 (d, J=5.4 Hz, 1H), 6.58 ( td, J=8.3, 2.6 Hz, 1H), 6.51 (dd, J=10.9, 2.5 Hz, 1H), 5.81 (dc, J=10.1, 6, 1 Hz, 1H), 4.63-4.43 (m, 2H), 3.87 (s, 3H), 3.75 (s, 3H), 2.38 (s, 3H), 2.15 ( s, 3H), 0.99 (d, J=7.1 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -113.59. 526

HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₈ H ₃₀ FN ₂ O ₆ , 509.2088; found 509,2079 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.47-8.36 (m, 1H), 8.31 (d, J=5.4 Hz, 1H), 7.35 (dd, J=8, 7, 5.7 Hz, 1H), 7.30-7.15 (m, 5H), 6.99 (d, J=5.5 Hz, 1H), 6.85 (td, J=8.4 , 2.8 Hz, 1H), 6.79 (dd, J=9.8, 2.8 Hz, 1H), 5.73 (dc, J=10.0, 6.1 Hz, 1H), 4 .60-4.47 (m, 1H), 4.26 (d, J=10.0 Hz, 1H), 3.89 (s, 3H), 2.38 (s, 3H), 2.30 ( s, 3H), 1.23 (d, J=6.1 Hz, 3H), 0.96 (d, J=7.1 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -117.14. 527

HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₉ H ₃₂ FN ₂ O ₇ , 539.2193; found 539.2180 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.41 (d, J=5.0 Hz, 1H), 8.30 (d, J=5.4 Hz, 1H), 7.23-7.19 (m, 2H), 7.19-7.10 (m, 1H), 7.03 (d, J=7.9 Hz, 2H), 6.97 (d, J=5.5 Hz, 1H) , 6.63-6.50 (m, 2H), 5.80 (dc, J=9.6, 6.1 Hz, 1H), 4.61-4.46 (m, 2H), 3.88 (s, 3H), 3.81 (s, 3H), 2.38 (s, 3H), 2.25 (s, 3H), 1.22 (d, J=6.2 Hz, 3H), 0 .95 (d, J=7.2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -113.44. 528

HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₉ H ₃₂ FN ₂ O ₆ , 523.2244; found 523.2235 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.40 (d, J=8.6 Hz, 1H), 8.31 (d, J=5.4 Hz, 1H), 7.28 (dd, J =8.8, 5.9 Hz, 1H), 7.18-7.10 (m, 2H), 7.02 (d, J=7.9 Hz, 2H), 6.98 (d, J= 5.5 Hz, 1H), 6.92-6.78 (m, 2H), 5.74 (dc, J=10.0, 6.1 Hz, 1H), 4.62-4.45 (m , 1H), 4.24 (d, J=10.1 Hz, 1H), 3.88 (s, 3H), 2.38 (s, 3H), 2.37 (s, 3H), 2.24 (s, 3H), 1.24 (d, J=6.1 Hz, 3H), 0.97 (d, J=7.2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -116.88. 529

HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₉ H ₃₂ FN ₂ O ₇ , 539.2193; found 539.2182 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.41 (d, J=7.9 Hz, 1H), 8.31 (d, J=5.4 Hz, 1H), 7.37-7.23 (m, 1H), 7.20-7.12 (m, 2H), 7.06 (d, J=7.8 Hz, 2H), 6.98 (d, J=5.5 Hz, 1H) , 6.57 (td, J=8.3, 2.5 Hz, 1H), 6.50 (dd, J=11.0, 2.6 Hz, 1H), 5.78 (dc, J=10 .2, 6.1 Hz, 1H), 4.69-4.41 (m, 2H), 3.89 (s, 3H), 3.76 (s, 3H), 2.38 (s, 3H) , 2.27 (s, 3H), 1.21 (d, J=6.1 Hz, 3H), 0.98 (d, J=7.1 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -113.82. 530

HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₉ H ₃₂ FN ₂ O ₆ , 523.2244; found 523,2229 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.40 (s, 1H), 8.30 (d, J=5.4 Hz, 1H), 7.33 (dd, J=8.7.5, 8 Hz, 1H), 7.20-7.04 (m, 4H), 6.98 (d, J=5.5 Hz, 1H), 6.84 (td, J=8.5, 2.9 Hz, 1H), 6.77 (dd, J=9.6, 2.4 Hz, 1H), 5.71 (dc, J=10.1, 6.1 Hz, 1H), 4.61-4 .45 (m, 1H), 4.21 (d, J=10.1 Hz, 1H), 3.89 (s, 3H), 2.38 (s, 3H), 2.30 (s, 3H) , 2.28 (s, 3H), 1.23 (d, J=6.0 Hz, 3H), 0.96 (d, J=7.2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -117.33. 531

HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₈ H ₂₉ F ₂ N ₂ O ₇ , 543.1943; found 543,1936 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.40 (d, J=6.0 Hz, 1H), 8.30 (d, J=5.5 Hz, 1H), 7.35-7.22 (m, 2H), 7.13 (dd, J=8.3, 6.4 Hz, 1H), 6.99 (d, J=5.5 Hz, 1H), 6.96-6.84 ( m, 2H), 6.65-6.51 (m, 2H), 5.79 (dc, J=9.7, 6.2 Hz, 1H), 4.64-4.47 (m, 2H) , 3.88 (s, 3H), 3.81 (s, 3H), 2.38 (s, 3H), 1.23 (d, J=6.1 Hz, 3H), 0.99 (d, J=7.2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -112.92, -116.48. 532

HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₈ H ₂₉ F ₂ N ₂ O ₆ , 527.1993; found 527,1984 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.39 (d, J=8.2 Hz, 1H), 8.31 (d, J=5.4 Hz, 1H), 7.29-7.19 (m, 3H), 6.99 (d, J=5.5 Hz, 1H), 6.94-6.81 (m, 4H), 5.71 (dc, J=10.1, 6.1 Hz, 1H), 4.60-4.49 (m, 1H), 4.26 (d, J=10.0 Hz, 1H), 3.89 (s, 3H), 2.38 (s, 3H ), 2.35 (s, 3H), 1.25 (d, J=6.2 Hz, 3H), 1.02 (d, J=7.2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -116.02, -116.38. 533

HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₈ H ₂₉ F ₂ N ₂ O ₇ , 543.1943; found 543,1928 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.41 (d, J=5.8 Hz, 1H), 8.30 (d, J=5.4 Hz, 1H), 7.33-7.18 (m, 3H), 7.02-6.89 (m, 3H), 6.58 (td, J=8.4, 2.5 Hz, 1H), 6.52 (dd, J=10.9 , 2.6 Hz, 1H), 5.76 (dc, J=10.0, 6.2 Hz, 1H), 4.60-4.46 (m, 2H), 3.88 (s, 3H) , 3.75 (s, 3H), 2.38 (s, 3H), 1.21 (d, J=6.2 Hz, 3H), 1.01 (d, J=7.2 Hz, 3H) .
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -113.26, -116.11. 534

HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₈ H ₂₉ F ₂ N ₂ O ₆ , 527.1993; found 527,1985 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.40 (d, J=8.1 Hz, 1H), 8.30 (d, J=5.4 Hz, 1H), 7.33 (dd, J = 8.6, 5.7 Hz, 1H), 7.23-7.13 (m, 2H), 7.04-6.92 (m, 3H), 6.86 (td, J=8.5 , 2.8 Hz, 1H), 6.80 (dd, J=9.7, 2.8 Hz, 1H), 5.69 (dc, J=9.9, 6.2 Hz, 1H), 4 .63-4.45 (m, 1H), 4.24 (d, J=9.8 Hz, 1H), 3.89 (s, 3H), 2.38 (s, 3H), 2.28 ( s, 3H), 1.23 (d, J=6.1 Hz, 3H), 0.99 (d, J=7.2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -115.54, -116.80. 535

(Thin film) 3385, 2982, 1771, 1737, 1679, 1605, 1508 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₉ H ₃₃ N ₂ O ₆ , 505.233; found 505.2333 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.49-8.39 (m, 1H), 8.30 (d, J=5.5 Hz, 1H), 7.19-7.05 (m, 6H), 7.01-6.92 (m, 3H), 5.78 (dc, J=10.2, 6.1 Hz, 1H), 4.59-4.46 (m, 1H), 3 .96 (d, J=10.2 Hz, 1H), 3.86 (s, 3H), 2.37 (s, 3H), 2.30 (s, 3H), 2.27 (s, 3H) , 1.23 (d, J=6.2 Hz, 3H), 0.90 (d, J=7.2 Hz, 3H). 536

(Thin Film) 3377, 2985, 1771, 1736, 1677, 1502, 1195 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₉ H ₃₁ F ₂ N ₂ O ₇ , 557.2094; found 557,2082 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.41 (d, J=5.6 Hz, 1H), 8.31 (d, J=5.4 Hz, 1H), 7.23 (dd, J =8.5, 6.6 Hz, 1H), 7.16 (dd, J=8.6, 5.9 Hz, 1H), 6.99 (d, J=5.5 Hz, 1H), 6 .81 (cd, J=9.1, 8.3, 2.8 Hz, 2H), 6.57 (td, J=8.3, 2.5 Hz, 1H), 6.51 (dd, J =10.8, 2.5 Hz, 1H), 5.68 (dc, J=10.0, 6.1 Hz, 1H), 4.74 (d, J=10.0 Hz, 1H), 4 .62-4.49 (m, 1H), 3.90 (s, 3H), 3.76 (s, 3H), 2.42 (s, 3H), 2.38 (s, 3H), 1, 21 (d, J=5.9 Hz, 3H), 1.04 (d, J=7.2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -113.52, -117.02. 537

(Thin Film) 3376, 2940, 1770, 1737, 1678, 1601, 1502, 1196 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₈ H ₂₈ F ₃ N ₂ O ₇ , 561.1843; found 561,1836 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.40 (d, J=6.1 Hz, 1H), 8.31 (d, J=5.4 Hz, 1H), 7.31 (dd, J =8.4, 6.7 Hz, 1H), 7.23-7.14 (m, 1H), 6.99 (d, J=5.5 Hz, 1H), 6.84-6.68 ( m, 2H), 6.58 (td, J=8.3, 2.5 Hz, 1H), 6.52 (dd, J=10.8, 2.5 Hz, 1H), 5.86-5 .73 (m, 1H), 4.78 (d, J=9.9 Hz, 1H), 4.65-4.43 (m, 1H), 3.90 (s, 3H), 3.75 ( s, 3H), 2.38 (s, 3H), 1.24 (d, J=6.1 Hz, 3H), 1.04 (d, J=7.2 Hz, 3H). 538

(Thin Film) 3378, 2986, 1770, 1736, 1677, 1501, 1196 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₉ H ₃₁ F ₂ N ₂ O ₇ , 557.2094; found 557,2091 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.44-8.37 (m, 1H), 8.31 (d, J=5.4 Hz, 1H), 7.33 (dd, J=8, 5, 5.8 Hz, 1H), 7.04 (dd, J=8.4, 6.8 Hz, 1H), 6.99 (d, J=5.5 Hz, 1H), 6.88- 6.74 (m, 2H), 6.64-6.53 (m, 2H), 5.67 (dc, J=9.8, 6.1 Hz, 1H), 4.74 (d, J= 9.8 Hz, 1H), 4.62-4.45 (m, 1H), 3.90 (s, 3H), 3.84 (s, 3H), 2.38 (s, 3H), 2, 27 (s, 3H), 1.25 (d, J=6.2 Hz, 3H), 0.98 (d, J=7.2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -112.97, -117.43. 539

(Thin film) 3377, 2983, 1771, 1738, 1677, 1502, 1201 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₈ H ₂₈ F ₃ N ₂ O ₆ , 545.1894; found 545,1896 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.43-8.35 (m, 1H), 8.31 (d, J=5.4 Hz, 1H), 7.33 (dd, J=8, 6, 5.7 Hz, 1H), 7.19-7.07 (m, 1H), 7.00 (d, J=5.5 Hz, 1H), 6.90-6.74 (m, 4H ), 5.68 (dc, J=12.0, 6.1 Hz, 1H), 4.62 (d, J=9.9 Hz, 1H), 4.61-4.49 (m, 1H) , 3.90 (s, 3H), 2.38 (s, 3H), 2.28 (s, 3H), 1.27 (d, J=6.1 Hz, 3H), 1.00 (d, J=7.2 Hz, 3H). 540

(Thin film) 3388, 2985, 1771, 1737, 1679, 1572, 1508, 1452 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₈ H ₃₀ FN ₂ O ₆ , 509.2082; found 509,2078 ¹ H NMR (300 MHz, CDCl ₃ ) δ 8.43 (d, J=8.0 Hz, 1H), 8.31 (d, J=5.4 Hz, 1H), 7.37-7.21 (m, 5H), 7.24-7.14 (m, 1H), 6.98 (d, J=5.5 Hz, 1H), 6.89-6.84 (m, 1H), 6, 79-6.72 (m, 1H), 5.90-5.72 (m, 1H), 4.56 (dc, J=8.1, 7.1 Hz, 1H), 4.41 (d, J=10.0Hz, 1H), 3.89(s, 3H), 2.38(s, 3H), 2.24(s, 3H), 1.24(d, J=6.2Hz, 3H), 1.00 (d, J=7.2 Hz, 3H). 541

(Thin Film) 3378, 2984, 1771, 1737, 1679, 1509 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₈ H ₂₉ F ₂ N ₂ O ₆ , 527.1988; found 527,1975 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.42 (d, J=8.2 Hz, 1H), 8.31 (dd, J=5.5, 1.2 Hz, 1H), 7.29 -7.17 (m, 3H), 7.07-6.89 (m, 3H), 6.87 (dd, J=8.0, 1.7 Hz, 1H), 6.80-6.72 (m, 1H), 5.75 (dc, J=9.7, 6.1 Hz, 1H), 4.62-4.50 (m, 1H), 4.39 (d, J=9.8 Hz, 1H), 3.89 (s, 3H), 2.38 (s, 3H), 2.25 (s, 3H), 1.26-1.21 (m, 3H), 1.01 (d , J=7.2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -115.67, -118.89. 542

(Thin film) 3390, 2984, 1772, 1737, 1678, 1508, 1452 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₉ H ₃₂ FN ₂ O ₆ , 523.2239; found 523,2241 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.48-8.36 (m, 1H), 8.29 (d, J=5.6 Hz, 1H), 7.26-7.21 (m, 1H), 7.20-7.16 (m, 2H), 7.07 (d, J=7.9 Hz, 2H), 6.96 (d, J=5.5 Hz, 1H), 6, 84 (dd, J=8.1, 1.9 Hz, 1H), 6.74 (dd, J=11.3, 2.2 Hz, 1H), 5.83-5.73 (m, 1H) , 4.63-4.50 (m, 1H), 4.37 (d, J=10.1 Hz, 1H), 3.86 (s, 3H), 2.37 (s, 3H), 2, 27 (s, 3H), 2.22 (s, 3H), 1.24 (d, J=6.1 Hz, 3H), 1.00 (d, J=7.2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -119.02. 543

(Thin film) 3384, 2983, 1772, 1737, 1679, 1591, 1507, 1452 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₉ H ₃₁ F ₂ N ₂ O ₆ , 541.2145; found 541,2138 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.42 (d, J=7.9 Hz, 1H), 8.31 (d, J=5.4 Hz, 1H), 7.24 (dd, J =9.6, 5.7 Hz, 1H), 7.17 (t, J=7.9 Hz, 1H), 6.99 (d, J=5.5 Hz, 1H), 6.88-6 .82 (m, 3H), 6.75 (dd, J=11.3, 2.2 Hz, 1H), 5.72 (dc, J=9.8, 6.1 Hz, 1H), 4, 63 (d, J=10.0 Hz, 1H), 4.62-4.51 (m, 1H), 3.89 (s, 3H), 2.39 (s, 3H), 2.38 (s , 3H), 2.24 (s, 3H), 1.26 (d, J=6.1 Hz, 3H), 1.05 (d, J=7.2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -116.51, -118.10. 544

(Thin film) 3381, 2984, 1771, 1739, 1678, 1504, 1453, 1432 HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₈ H ₂₈ F ₃ N ₂ O ₆ ; 545.1894; found 545,1885 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.45-8.39 (m, 1H), 8.31 (d, J=5.5 Hz, 1H), 7.32-7.20 (m, 2H), 6.99 (d, J=5.5 Hz, 1H), 6.88-6.84 (m, 1H), 6.84-6.73 (m, 3H), 5.85-5 .74 (m, 1H), 4.70 (d, J=9.9 Hz, 1H), 4.63-4.52 (m, 1H), 3.89 (s, 3H), 2.38 ( s, 3H), 2.25 (s, 3H), 1.27 (d, J=6.1 Hz, 3H), 1.04 (d, J=7.2 Hz, 3H). 545

(Thin Film) 3378, 2982, 1770, 1734, 1675, 1508, 1451, 1309, 1200, 1174, 1046, 907, 802, 730, 699 ESIMS m/z 491.2 ([M+H] ⁺ ) ¹ H NMR (500 MHz, CDCl ₃ ) δ 8.41 (s, 1H), 8.32 (d, J=5.5 Hz, 1H), 7.31-7.27 (m, 2H), 7 .22 (t, J=7.7 Hz, 2H), 7.17 (d, J=8.1 Hz, 2H), 7.15-7.10 (m, 1H), 7.09 (d, J=7.9 Hz, 2H), 6.99 (d, J=5.5 Hz, 1H), 5.79 (dc, J=10.1, 6.1 Hz, 1H), 4.57- 4.47 (m, 1H), 4.01 (d, J=10.1 Hz, 1H), 3.90 (s, 3H), 2.38 (s, 3H), 2.28 (s, 3H ), 1.24 (d, J=6.2 Hz, 3H), 0.88 (d, J=7.2 Hz, 3H).
¹³ C NMR (126 MHz, CDCl ₃ ) δ 172.24, 168.91, 162.24, 159.40, 146.64, 141.73, 141.57, 138.27, 137.43, 136.47 , 129.44, 128.46, 127.99, 126.56, 109.68, 73.36, 57.53, 56.27, 47.83, 20.97, 20.75, 19.24, 17 .92. 546

(Thin Film) 3381, 2982, 1770, 1734, 1675, 1507, 1435, 1309, 1199, 1174, 1045, 907, 804, 729, 699 ESIMS m/z 491.2 ([M+H] ⁺ ) ¹ H NMR (500 MHz, CDCl ₃ ) δ 8.42 (s, 1H), 8.32 (d, J=5.4 Hz, 1H), 7.29-7.23 (m, 4H), 7 .18 (td, J=6.0, 2.8Hz, 3H), 7.04 (d, J=7.9Hz, 2H), 6.99 (d, J=5.5Hz, 1H) , 5.79 (dc, J=9.8, 6.2 Hz, 1H), 4.57-4.49 (m, 1H), 4.02 (d, J=9.9 Hz, 1H), 3.90 (s, 3H), 2.38 (s, 3H), 2.25 (s, 3H), 1.23 (d, J=6.2 Hz, 3H), 0.93 (d, J =7.2 Hz, 3H).
¹³ C NMR (126 MHz, CDCl ₃ ) δ 172.23, 168.92, 162.25, 159.41, 146.64, 141.59, 138.34, 137.44, 136.15, 129.13 , 128.72, 128.09, 127.99, 126.77, 109.68, 73.38, 57.41, 56.28, 47.87, 20.94, 20.76, 19.25, 18 .00 547

(Thin Film) 3380, 2982, 1770, 1735, 1676, 1507, 1451, 1310, 1200, 1175, 1158, 1047, 908, 816, 769, 729 ESIMS m/z 509.1 ([M+H] ⁺ ) ¹ H NMR (500 MHz, CDCl ₃ ) δ 8.41 (s, 1H), 8.32 (d, J=5.4 Hz, 1H), 7.23 (dd, J=8.7.5, 3 Hz, 2H), 7.18-7.13 (m, 2H), 7.05 (d, J=7.8 Hz, 2H), 7.01-6.93 (m, 3H), 5, 74 (dc, J=9.6, 6.2 Hz, 1H), 4.58-4.50 (m, 1H), 4.01 (d, J=9.6 Hz, 1H), 3.90 (s, 3H), 2.38 (s, 3H), 2.26 (s, 3H), 1.22 (d, J=6.2 Hz, 3H), 0.94 (d, J=7, 2 Hz, 3H).
¹³ C NMR (126 MHz, CDCl ₃ ) δ 172.18, 168.91, 162.26, 161.64 (d, J=245.3 Hz), 159.43, 146.63, 141.54, 138 .05, 137.45, 137.32 (d, J=3.3 Hz), 136.34, 129.56 (d, J=7.8 Hz), 129.22, 127.94, 115.53 (d, J=21.3 Hz), 109.70, 73.21, 56.51, 56.28, 47.85, 20.94, 20.75, 19.15, 17.99. 548

(Thin Film) 3379, 2983, 1770, 1736, 1676, 1509, 1452, 1310, 1201, 1175, 1046, 908, 817, 732, 700 ESIMS m/z 495.1 ([M+H] ⁺ ) ¹ H NMR (500 MHz, CDCl ₃ ) δ 8.40 (s, 1H), 8.32 (d, J=5.4 Hz, 1H), 7.33-7.23 (m, 6H), 7 .23-7.17 (m, 1H), 6.99 (d, J=5.5 Hz, 1H), 6.93 (t, J=8.6 Hz, 2H), 5.76 (dc, J=9.9, 6.2Hz, 1H), 4.55(p, J=7.2Hz, 1H), 4.05(d, J=9.8Hz, 1H), 3.90( s, 3H), 2.38 (s, 3H), 1.23 (d, J=6.2 Hz, 3H), 0.97 (d, J=7.2 Hz, 3H).
¹³ C NMR (126 MHz, CDCl ₃ ) δ 172.17, 168.91, 162.28, 161.59 (d, J=245.0 Hz), 159.44, 146.64, 141.48, 141 .04, 137.47, 137.16 (d, J=3.4 Hz), 129.60 (d, J=7.9 Hz), 128.84, 128.02, 127.02, 115.28 (d, J=21.1 Hz), 109.74, 73.24, 57.00, 56.28, 47.83, 20.75, 19.22, 18.02. 549

(Thin Film) 3380, 2983, 1770, 1735, 1676, 1507, 1451, 1436, 1310, 1201, 1175, 1046, 908, 816, 731 ESIMS m/z 509.1 ([M+H] ⁺ ) ¹ H NMR (500 MHz, CDCl ₃ ) δ 8.39 (s, 1H), 8.32 (d, J=5.5 Hz, 1H), 7.28-7.21 (m, 2H), 7 .14 (d, J=8.2 Hz, 2H), 7.09 (d, J=7.9 Hz, 2H), 6.99 (d, J=5.5 Hz, 1H), 6.95 -6.89 (m, 2H), 5.74 (dc, J=10.0, 6.2 Hz, 1H), 4.58-4.50 (m, 1H), 4.00 (d, J =10.0 Hz, 1H), 3.90 (s, 3H), 2.38 (s, 3H), 2.29 (s, 3H), 1.23 (d, J=6.1 Hz, 3H ), 0.97 (d, J=7.1 Hz, 3H).
¹³ C NMR (126 MHz, CDCl ₃ ) δ 172.18, 168.91, 162.27, 161.54 (d, J=245.1 Hz), 159.44, 146.63, 141.50, 138 .06, 137.48 (d, J=3.6 Hz), 136.65, 129.49 (d, J=8.3 Hz), 127.86, 115.24 (d, J=21.3 Hz), 109.73, 73.30, 56.66, 56.28, 47.83, 20.98, 20.75, 19.22, 18.02. 550

(Thin Film) 3380, 2984, 1770, 1737, 1676, 1503, 1452, 1310, 1200, 1175, 1148, 1048, 907, 731 ESIMS m/z 513.2 ([M+H] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.39 (d, J=8.1 Hz, 1H), 8.32 (d, J=5.5 Hz, 1H), 7.34-7.22 (m, 5H), 7.20-7.14 (m, 1H), 6.99 (d, J=5.5 Hz, 1H), 6.85-6.74 (m, 2H), 5, 80 (dtd, J=9.9, 7.3, 6.7, 5.4 Hz, lH), 4.55 (dt, J=8.1, 7.1 Hz, 1H), 4.41 ( d, J=10.0 Hz, 1H), 3.90 (s, 3H), 2.38 (s, 3H), 1.27 (d, J=6.1 Hz, 3H), 0.92 ( e, J=7.2 Hz, 3H).
¹³ C NMR (126 MHz, CDCl ₃ ) δ 172.13, 168.91, 162.27, 162.03 (dd, J=168.8, 12.1 Hz), 160.96-159.14 (m ), 159.43, 146.64, 141.50, 140.06, 137.46, 129.88 (dd, J=9.6, 5.6 Hz), 128.60, 128.27, 126, 99, 124.68-124.00 (m), 111.60 (dd, J=21.3, 3.6 Hz), 109.72, 104.55-103.34 (m), 72.51, 56.28, 49.35, 47.80, 20.75, 18.92, 17.92. 551

(Thin Film) 3384, 2983, 1771, 1737, 1677, 1502, 1452, 1310, 1201, 1175, 1148, 1049, 966, 908, 732 ESIMS m/z 527.2 ([M+H] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.40 (s, 1H), 8.32 (d, J=5.5 Hz, 1H), 7.25-7.16 (m, 3H), 7 .05 (d, J=7.9 Hz, 2H), 6.99 (d, J=5.5 Hz, 1H), 6.84-6.73 (m, 2H), 5.77 (dtd, J=9.5, 6.5, 5.2 Hz, 1H), 4.59-4.51 (m, 1H), 4.38 (d, J=9.8 Hz, 1H), 3.90 (s, 3H), 2.38 (s, 3H), 2.26 (s, 3H), 1.25 (d, J=6.2 Hz, 3H), 0.96 (d, J=7, 2 Hz, 3H).
¹³ C NMR (126 MHz, CDCl ₃ ) δ 172.12, 168.92, 162.78-159.09 (m), 146.64, 141.53, 137.46, 136.96, 136.56, 129.88 (d, J=5.7 Hz), 129.24, 128.16, 124.64 (d, J=15.0 Hz), 111.52 (d, J=20.8 Hz), 109.71, 104.49-103.84 (m), 72.59, 56.28, 48.90, 47.84, 20.96, 20.75, 18.92, 18.00. 552

(Thin Film) 3384, 2985, 1770, 1737, 1676, 1503, 1201, 1175, 1160, 1148, 966, 847, 825, 811, 732 ESIMS m/z 531.2 ([M+H] ⁺ ) ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.37 (d, J=6.0 Hz, 1H), 8.32 (d, J=5.4 Hz, 1H), 7.28-7.18 (m, 3H), 7.00 (d, J=5.5 Hz, 1H), 6.97-6.90 (m, 2H), 6.86-6.75 (m, 2H), 5, 76 (dtd, J=9.7, 6.5, 5.2 Hz, 1H), 4.62-4.48 (m, 1H), 4.39 (d, J=9.8 Hz, 1H) , 3.91 (s, 3H), 2.38 (s, 3H), 1.26 (d, J=6.1 Hz, 3H), 1.00 (d, J=7.2 Hz, 3H) .
¹³ C NMR (126 MHz, CDCl ₃ ) δ 172.05, 168.91, 163.09-159.02 (m), 146.63, 141.42, 137.50, 135.78, 129.82 ( d, J=8.2 Hz), 124.23 (d, J=11.3 Hz), 115.42 (d, J=21.3 Hz), 111.98-111.29 (m), 109 .77, 104.80-103.42 (m), 72.42, 56.30, 48.69, 47.81, 20.75, 18.93, 18.00. 553

HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₈ H ₃₀ FN ₂ O ₆ , 509.2088; found 509,2074 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.41 (d, J=7.4 Hz, 1H), 8.31 (d, J=5.4 Hz, 1H), 7.32-7.20 (m, 4H), 7.19-7.11 (m, 1H), 7.12-7.02 (m, 2H), 6.98 (d, J=5.5 Hz, 1H), 6, 90 (dd, J=9.6, 8.1 Hz, 1H), 5.76 (dc, J=10.0, 6.2 Hz, 1H), 4.59-4.45 (m, 1H) , 3.99 (d, J=10.1 Hz, 1H), 3.88 (s, 3H), 2.37 (s, 3H), 2.22 (d, J=2.0Uz, 3H), 1.23 (d, J=6.1 Hz, 3H), 0.90 (d, J=7.2 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -120.17. 554

HRMS-ESI (m/z) ([M+H] ⁺ ) calculated for C ₂₉ H ₃₁ F ₂ N ₂ O ₇ , 557.2099; found 557,2091 ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.40 (s, 1H), 8.31 (d, J=5.4 Hz, 1H), 7.32-7.23 (m, 1H), 7 .11-7.01 (m, 2H), 6.99 (d, J=5.5 Hz, 1H), 6.88 (t, J=9.3 Hz, lH), 6.58 (td, J=8.3, 2.5 Hz, 1H), 6.52 (dd, J=10.9, 2.5 Hz, 1H), 5.74 (dc, J=10.1, 6.2 Hz , 1H), 4.55 (dc, J=8.1, 7.2 Hz, 1H), 4.46 (d, J=10.1 Hz, 1H), 3.90 (s, 3H), 3 .77 (s, 3H), 2.38 (s, 3H), 2.21 (d, J=1.9 Hz, 3H), 1.20 (d, J=6.1 Hz, 3H), 0 .99 (d, J=7.1 Hz, 3H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -113.46, -120.45.

conn. no. - connection number

Table 3. Biological testing scale

Evaluation table for fungal pathogens % control Grade > 80 A ≤ 80 B Not tested C Activity was not observed in the above assay D

Table 4. Biological activity - disease control of PUCCRT and SEPTTR in high and low volume applications

HV activity at 100 ppm LV activity at 121.5 g/ha PUCCRT* SEPTTR* PUCCRT* SEPTTR* conn. no. 1DP* 3DC* 1DP* 3DC* 1DP* 3DC* 1DP* 3DC* 89 C C C C C WITH C WITH 90 A A A A C WITH WITH WITH 91 A B A D C WITH WITH WITH 92 A A A A A IN A A 93 B D A B C WITH C C 95 C C C C C WITH WITH WITH 96 A A A A C WITH WITH WITH 97 B D A A WITH WITH WITH WITH 98 A A A A WITH WITH WITH WITH 99 A B A A WITH WITH WITH WITH 100 A A A A WITH WITH WITH WITH 101 D D B D WITH WITH WITH WITH 102 B D B B WITH WITH WITH WITH 103 A B A A WITH WITH WITH WITH 104 A D B A WITH WITH WITH WITH 105 A A A A WITH WITH WITH WITH 106 A D A A WITH WITH WITH WITH 107 A B A A WITH WITH WITH WITH 109 B D D B WITH WITH WITH WITH 110 A D A A C C C C 111 B D B A C C C C 112 D D B B C C C C 113 A B A IN C WITH C WITH 114 A A A A C WITH C WITH 115 B D A A C WITH C WITH 116 B D B B C WITH C WITH 117 A B A A C WITH C WITH 118 A A B A WITH WITH C WITH 119 D D A B WITH WITH C WITH 120 A B A A WITH WITH C WITH 121 A B A A WITH WITH WITH WITH 122 D D B B WITH WITH WITH WITH 123 B D B A WITH WITH WITH WITH 124 A A A A WITH WITH WITH WITH 125 A A A A WITH WITH WITH WITH 127 B D B D WITH WITH WITH WITH 128 B D A B WITH WITH WITH WITH 129 A B A A WITH WITH WITH WITH 130 B D A D WITH WITH WITH WITH 131 A D A A WITH WITH WITH WITH 132 A B A A WITH WITH WITH WITH 133 A A A A WITH WITH WITH WITH 135 B D B D WITH WITH WITH WITH 136 A B A B WITH WITH WITH WITH 137 A B A A WITH WITH WITH WITH 138 C C C C D IN A IN 139 C C C C A A A A 140 C C C C A IN A A 141 WITH C WITH WITH A A A A 142 WITH C WITH WITH A A A A 143 WITH C WITH WITH B D D B 144 WITH C WITH WITH IN B B IN 145 WITH C WITH WITH A A A A 146 WITH C WITH WITH A A A A 147 WITH C WITH WITH B B B A 148 WITH C WITH WITH A A A A 149 C WITH WITH WITH B B A A 150 C WITH WITH WITH A A A A 152 C WITH WITH WITH B B A A 153 C WITH WITH WITH B B A A 155 C WITH WITH WITH A A A A 156 C WITH WITH WITH A A A A 157 C WITH WITH WITH A A A A 158 C WITH WITH WITH A A A A 159 WITH WITH WITH WITH A A A A 160 WITH WITH WITH WITH A B A A 161 WITH WITH WITH WITH D D B A 162 WITH WITH WITH WITH D D D B 163 WITH WITH WITH WITH B D B A 164 WITH WITH WITH WITH D D B D 165 WITH WITH WITH WITH A B A A 166 WITH WITH WITH WITH B D B B 167 WITH WITH WITH WITH A A A A 168 WITH WITH WITH WITH A B A A 169 WITH WITH WITH WITH A B A A 170 WITH WITH WITH WITH B B B B 171 WITH WITH WITH WITH A A A A 173 WITH WITH WITH WITH A B A A 174 WITH WITH WITH WITH A IN A A 175 WITH WITH WITH WITH A A A A 176 WITH WITH WITH WITH A A A A 178 WITH WITH WITH WITH B D A A 179 WITH WITH WITH WITH B D A A 180 WITH WITH WITH WITH D D B D 181 WITH WITH WITH WITH D D B B 182 WITH WITH WITH WITH D B D B 183 WITH WITH WITH WITH A A A B 184 WITH WITH WITH WITH A A A A 185 WITH WITH WITH WITH A B A A 186 WITH WITH WITH WITH B D A B 187 WITH WITH WITH WITH A B B B 188 WITH WITH WITH WITH A B A A 189 WITH WITH WITH WITH A B A A 190 C WITH WITH WITH B D B B 191 C WITH WITH WITH A A A A 192 C WITH WITH WITH A A A A 193 C WITH WITH WITH B D A A 194 C WITH WITH WITH A B A A 195 C WITH WITH WITH A B A B 196 C WITH WITH WITH D D A B 197 C WITH WITH WITH A A A A 198 WITH WITH WITH WITH A B A A 199 WITH WITH WITH WITH A A A A 201 WITH WITH WITH WITH B D A A 202 WITH WITH WITH WITH D D A A 203 WITH WITH WITH WITH A B A A 204 WITH WITH WITH WITH A A A A 206 WITH WITH WITH WITH A B A A 207 WITH WITH WITH WITH D D A A 208 WITH WITH WITH WITH A B A A 209 WITH WITH WITH WITH A B A A 210 WITH WITH WITH WITH A B A A 211 WITH WITH WITH WITH A A A A 212 WITH WITH WITH WITH A A A A 213 WITH WITH WITH WITH B B A A 214 WITH WITH WITH WITH D D D D 215 WITH WITH WITH WITH A D A A 216 WITH WITH WITH WITH A B A B 217 WITH WITH WITH WITH A B A A 218 WITH WITH WITH WITH A B A A 219 WITH WITH WITH WITH A D A A 220 WITH WITH WITH WITH A B A A 221 WITH WITH WITH WITH B D B A 222 WITH WITH WITH WITH A D A A 223 WITH WITH WITH WITH B D B B 224 WITH WITH WITH WITH B D A A 225 WITH WITH WITH WITH D D D D 228 WITH WITH WITH WITH C C C C 229 WITH WITH WITH WITH D D D B 230 WITH WITH WITH WITH D D D D 386 IN D IN D C C C C 387 A IN A IN C C C C 388 B B A A C WITH WITH WITH 389 A D D D C WITH WITH WITH 390 A B A D C WITH WITH WITH 391 A A A A C WITH WITH WITH 392 A B A D C WITH WITH WITH 393 C C C C C WITH WITH WITH 394 B D A B C WITH WITH WITH 395 A A A A C WITH WITH WITH 396 A A A A C WITH WITH WITH 397 A D A A WITH WITH WITH WITH 398 B B B B WITH WITH WITH WITH 399 A A A A WITH WITH WITH WITH 400 A A A A WITH WITH WITH WITH 401 A B A A WITH WITH WITH WITH 402 A B A B WITH WITH WITH WITH 403 A B A A WITH WITH WITH WITH 404 A A A A WITH WITH WITH WITH 405 A A A A WITH WITH WITH WITH 406 A A A A WITH WITH WITH WITH 407 A A A A WITH WITH WITH WITH 408 A B A A WITH WITH WITH WITH 409 A D A A WITH WITH WITH WITH 410 B D B B WITH WITH WITH WITH 411 A B A A WITH WITH WITH WITH 412 C C C C WITH WITH WITH WITH 413 A B A A WITH WITH WITH WITH 414 B D A B WITH WITH WITH WITH 415 A B A A WITH WITH WITH WITH 416 A D A B WITH WITH WITH WITH 417 A D B B WITH WITH WITH WITH 418 A A A A WITH WITH WITH WITH 419 B D B B WITH WITH WITH WITH 420 B D B D WITH WITH WITH WITH 421 D D D D WITH WITH WITH WITH 422 D D B D WITH WITH WITH WITH 423 A A A A WITH WITH WITH WITH 424 A B A A WITH WITH WITH WITH 425 A A A A WITH WITH WITH WITH 426 A D A A WITH WITH WITH WITH 427 B D B B C WITH WITH WITH 428 B D B A C WITH WITH WITH 429 B D B B C WITH WITH WITH 430 A B A A C WITH WITH WITH 431 A A A A C WITH WITH WITH 432 B A A A C WITH WITH WITH 433 A A A A C WITH WITH WITH 434 A A A A C WITH WITH WITH 435 A A A A C WITH WITH WITH 436 A A A A WITH WITH WITH WITH 437 A A A A WITH WITH WITH WITH 438 A A A A WITH WITH WITH WITH 439 A A A A WITH WITH WITH WITH 440 A A A A WITH WITH WITH WITH 441 A B A A WITH WITH WITH WITH 442 A A A A WITH WITH WITH WITH 443 A A A A WITH WITH WITH WITH 444 A A A A WITH WITH WITH WITH 445 A B A A WITH WITH WITH WITH 446 A B A A WITH WITH WITH WITH 447 A A A A WITH WITH WITH WITH 448 A A A A WITH WITH WITH WITH 449 A A A A WITH WITH WITH WITH 450 A B A A WITH WITH WITH WITH 451 A A A A WITH WITH WITH WITH 452 A A A A WITH WITH WITH WITH 453 A A A A WITH WITH WITH WITH 454 A A A A WITH WITH WITH WITH 455 A A A A WITH WITH WITH WITH 456 A A A A WITH WITH WITH WITH 457 A A A A WITH WITH WITH WITH 458 A A A A WITH WITH WITH WITH 459 A A A A WITH WITH WITH WITH 460 A A A A WITH WITH WITH WITH 461 A A A A WITH WITH WITH WITH 462 C C C C D D D IN 463 C C C C D D D IN 464 C WITH WITH WITH A A A A 465 C WITH WITH WITH B D D D 466 C WITH WITH WITH B D A B 467 C WITH WITH WITH B B A B 468 C WITH WITH WITH A B A A 469 C WITH WITH WITH B D D D 470 C WITH WITH WITH IN B B B 471 C WITH WITH WITH A B A A 472 WITH WITH WITH WITH A A A A 473 WITH WITH WITH WITH B B A A 474 WITH WITH WITH WITH B D A A 475 WITH WITH WITH WITH A A A A 476 WITH WITH WITH WITH A A A A 477 WITH WITH WITH WITH B B A A 478 WITH WITH WITH WITH B D A B 479 WITH WITH WITH WITH D D A B 480 WITH WITH WITH WITH D B D D 481 WITH WITH WITH WITH B B B A 482 WITH WITH WITH WITH B A B A 483 WITH WITH WITH WITH B B A B 484 WITH WITH WITH WITH A B A B 485 WITH WITH WITH WITH A A A A 486 WITH WITH WITH WITH A B A A 487 WITH WITH WITH WITH A A B A 488 WITH WITH WITH WITH A B A A 489 WITH WITH WITH WITH A A A A 490 WITH WITH WITH WITH A B A A 491 WITH WITH WITH WITH A B A A 492 WITH WITH WITH WITH B B A A 493 WITH WITH WITH WITH B IN B B 494 WITH WITH WITH WITH B IN B B 495 WITH WITH WITH WITH IN IN B D 496 WITH WITH WITH WITH A IN A A 497 WITH WITH WITH WITH A IN A B 498 WITH WITH WITH WITH A IN A A 499 WITH WITH WITH WITH B D A A 500 WITH WITH WITH WITH A B A A 501 WITH WITH WITH WITH B B A B 502 C WITH WITH WITH A B B D 503 C WITH WITH WITH A B A A 504 C WITH WITH WITH A D B B 505 C WITH WITH WITH B D B D 506 C WITH WITH WITH D D D D 507 C WITH WITH WITH D D B D 508 C WITH WITH WITH A A A A 509 C WITH WITH WITH A B B B 510 WITH WITH WITH WITH A A A A 511 WITH WITH WITH WITH D B D D 512 WITH WITH WITH WITH D D D D 513 WITH WITH WITH WITH B D D D 514 WITH WITH WITH WITH D D D D 515 WITH WITH WITH WITH D D D D 516 WITH WITH WITH WITH A A A A 517 WITH WITH WITH WITH A B D B 518 WITH WITH WITH WITH A A A A 519 WITH WITH WITH WITH B B A B 520 WITH WITH WITH WITH D D D D 521 WITH WITH WITH WITH B B A B 522 WITH WITH WITH WITH B D A B 523 WITH WITH WITH WITH A A A A 524 WITH WITH WITH WITH A A A A 525 WITH WITH WITH WITH A A A A 526 WITH WITH WITH WITH A B A A 527 WITH WITH WITH WITH A B A A 528 WITH WITH WITH WITH A B A A 529 WITH WITH WITH WITH A IN A A 530 WITH WITH WITH WITH A D A A 531 WITH WITH WITH WITH A A A A 532 WITH WITH WITH WITH A A A A 533 WITH WITH WITH WITH A A A A 534 WITH WITH WITH WITH A B A A 535 WITH WITH WITH WITH A A A A 536 WITH WITH WITH WITH A B A A 537 WITH WITH WITH WITH A A A A 538 WITH WITH WITH WITH A B A A 539 WITH WITH WITH WITH A B A A 540 WITH WITH WITH WITH A B A A 541 C WITH WITH WITH A B A A 542 C WITH WITH WITH A B A A 543 C WITH WITH WITH A B A A 544 C WITH WITH WITH A A A A 545 C WITH WITH WITH A A A A 546 C WITH WITH WITH A A A A 547 C WITH WITH WITH A A A A 548 C WITH WITH WITH A A A A 549 WITH WITH WITH WITH A A A A 550 WITH WITH WITH WITH A A A A 551 WITH WITH WITH WITH A A A A 552 WITH WITH WITH WITH A A A A 553 WITH WITH WITH WITH A A A A 554 WITH WITH WITH WITH A A A A

*Comp. No. - connection number

*PUCCRT - Brown rust of wheat (Puccinia triticina)

*SEPTTR - Wheat leaf spot (Zymoseptoria tritici)

*1DP - 1 day. protective agent

*3DC - 3 days. Remedy

*g/ha - grams per hectare

*ppm - parts per million

Table 5. Biological activity - disease control at 100 ppm

ALTESO* CERCBE* COLLLA* LEPTNO* conn. no. 1DP* 92 B A A A 139 B A A A 140 A A A A 141 B A A A 142 A A A A 145 A A A A 146 A A A A 148 B A A A 150 A A A A 167 A A A A 171 B A A A 174 B A A A 176 B A A A 199 A A A A 204 A A A A 464 B A A A 468 A A A A 472 B A A A 475 B A A A 524 A A A A 528 B A A A 532 B A A A

conn. no. - connection number

ALTESO - Alternaria tomato (Alternaria solani)

CERCBE - sugar beet leaf spot (Cercospora beticola)

COLLLA - cucumber anthracnose (Colletotricum lagenarium)

LEPTNO - wheat septoria (Leptosphaeria nodorum)

*1DP - 1 day. protective agent

Table 6. Biological activity - disease control at 100 ppm

PYRIOR* RHYNSE* VENTIN* conn. no. 1DP* 92 C A C 139 A A A 140 A C A 141 A A A 142 A A A 145 A A A 146 A A A 148 A A A 150 A A A 167 A A C 171 A A C 174 A A B 176 A A A 199 A A C 204 A A WITH 464 A A A 468 A A A 472 A A A 475 A A B 524 A A A 528 A A A 532 C A C

conn. no. - connection number

PYRIOR - rice blast (Pyricularia oryzae)

RHYNSE - barley scorch (Rhyncosporium secalis)

VENTIN - apple scab (Venturia inaequalis)

*1DP - 1 day. protective agent

Table 7. Biological activity - disease control at 25 ppm

PHAKPA* conn. no. 1DP* 3DC* 139 A B 140 B D 141 A B 142 A B 92 B B 145 A B 146 A B 148 A B 150 A A 158 A B 167 A B 169 A D 171 A B 173 B D 174 A B 175 B D 176 B B 199 A B 204 A B 207 B D 208 A B 209 A B 210 A D 211 A B 212 B D 213 A B 464 A A 468 A B 472 A B 475 A B 493 D D 494 D D 495 B D 496 B D 497 D D 498 A B 499 B B 500 A B 501 B B 502 B D 503 A D 504 B D 505 D D 506 D D 507 D D 508 B D 509 D D 510 B D 511 D D 512 D D 513 D D 514 D D 515 D D 516 B D 517 B D 518 B D 519 D B 520 D D 521 B D 522 B D 523 A B 524 A B 525 A B 526 A D 527 A B 528 A B 529 A B 530 A B 531 A B 532 A B 533 A B 534 A B 535 B D 536 A B 537 A B 538 B B 539 A B 540 A B 541 A B 542 B D 543 A B 544 A B 545 B D 546 A B 547 A B 548 A D 549 B D 550 A B 551 A B 552 A B 553 B D 554 B D

conn. no. - connection number

PHAKPA - Asian soybean rust (Phakopsora pachyrhizi)

*1DP - 1 day. protective agent

*3DC - 3 days. Remedy.

Claims (3)

1. Compound of formula I

2. A method for controlling and preventing fungal infestation of a plant, wherein the method comprises the step of applying a fungicidally effective amount of a compound according to claim 1 to at least one of: a plant, an area adjacent to a plant, soil adapted to support plant growth, a plant root, and foliage plants.