A process for the preparation of phosphine- or carboxylate-containing axially chiral alkenyl boronates

Abstract

The application relates to a preparation method of phosphorus-containing or carboxylate-containing axially chiral alkenyl borate. Specifically, aryl 1,3-alkyne, aryl bromide containing phosphorus or carboxylate, an oxaphospholene as a ligand, and a diboron reagent are subjected to aryl boration of the alkyne under the condition of copper-palladium double catalysis to synthesize phosphorus-containing or carboxylate-containing axially chiral alkenyl borate with high corresponding selectivity. The synthesis method is simple in operation, and axially chiral alkenyl borate can be obtained in one step. The phosphorus-containing axially chiral alkenyl borate can be used to synthesize chiral phosphine-alkene ligands through a reduction reaction, and has good application prospect.

Description

Technical Field

[0001] This invention belongs to the field of organic synthesis technology, and specifically relates to a method for synthesizing axially chiral alkenyl borate esters containing phosphine or carboxylic esters. Background Technology

[0002] The enantioselective boration of 1,3-enynes to synthesize novel chiral organoboron compounds has attracted increasing attention from industry and academia, making it a valuable structural motif in asymmetric synthesis. However, previous studies have only demonstrated the feasibility of 1,2- or 1,4-difunctionalization of 1,3-enynes to deliver corresponding central chiral alkylboron compounds or axially chiral alkenylboron compounds. A method for synthesizing axially chiral 1,3-dienylboronic esters by asymmetrically catalyzing the 3,4-bifunctionalization of the carbon-carbon triple bond of 1,3-enynes has not yet been developed. The synthesis of phosphine-containing axially chiral 1,3-dienylboronic esters will provide convenient conditions for the preparation of novel chiral phosphine olefin ligands and has promising applications. Summary of the Invention

[0003] The purpose of this invention is to overcome the defects of the prior art and provide a method for efficiently preparing axially chiral alkenyl borate esters containing phosphine or carboxylic esters.

[0004] The technical solution of the present invention is as follows:

[0005] A method for synthesizing phosphine-containing axially chiral alkenyl borate esters includes the following steps:

[0006] (1) Add aryl-containing 1,3-enyne, phosphine-containing aryl bromide, copper salt, palladium, and ligand to a pressure-resistant sealed reaction vessel. Add diboron reagent and alkali in a glove box, remove air, fill with argon, add organic solvent, and stir the reaction at 40°C for 96 h.

[0007] (2) Take the material obtained in step (1) out of the pressure-resistant sealed reaction vessel, cool it to room temperature, add ethyl acetate and elute it with a short silica gel column to obtain the crude product, and extract the organic phase three times with water at 60°C; (3) evaporate the organic solvent in the organic phase obtained in step (2), purify it with a silica gel column, and then wash it with an eluent to obtain the phosphine-containing axially chiral alkenyl borate ester.

[0008] In a preferred embodiment of the present invention, the aryl-containing 1,3-enyne is one of the following: alkyl-substituted aryl-containing 1,3-enyne, aryl-containing 1,3-enyne without benzene ring substitution, aryl-containing 1,3-enyne with benzene ring substitution, and aryl-containing 1,3-enyne with polysubstituted benzene ring.

[0009] In a preferred embodiment of the present invention, the phosphine-containing aryl bromide is a phosphorus-containing aryl bromide with an unsubstituted benzene ring on the phosphine, a phosphorus-containing aryl bromide with a monosubstituted benzene ring on the phosphine, or a phosphorus-containing aryl bromide with a polysubstituted benzene ring on the phosphine.

[0010] In a preferred embodiment of the present invention, the copper salt is one of 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ethylene copper salt and 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ethylene copper salt.

[0011] A further preferred copper salt is 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-yl copper salt.

[0012] In a preferred embodiment of the present invention, the palladium catalyst is palladium acetate or palladium bromide.

[0013] A further preferred palladium catalyst is palladium acetate.

[0014] In a preferred embodiment of the present invention, the ligand is one of (R)-4-(anthra-9-yl)-3-(tert-butyl)-2,3-dihydrobenzo[d][1,3]oxophosphacyclopentadiene, (S)-3-(tert-butyl)-4-(2,6-dimethoxy-3,5-dimethylphenyl)-2,3-dihydrobenzo[d][1,3]oxophosphacyclopentadiene, and (3aS,8aR)-2-(m-methyl)-3a,8a-dihydro-8H-indene[1,2-d]dioxazole.

[0015] A further preferred ligand is (R)-4-(anthracite-9-yl)-3-(tert-butyl)-2,3-dihydrobenzo[d][1,3]oxophosphanecyclopentadiene.

[0016] In a preferred embodiment of the present invention, the diboron reagent is pinacol diborate.

[0017] In a preferred embodiment of the present invention, the alkali is one of sodium tert-amyl alcohol or sodium tert-butoxide.

[0018] A further preferred alkali is sodium tert-amyl alcohol.

[0019] In a preferred embodiment of the present invention, the organic solvent is one of mesitylene and trifluorotoluene.

[0020] A further preferred organic solvent is mesitylene.

[0021] In a preferred embodiment of the present invention, the eluent is a mixed solution of petroleum ether and ethyl acetate.

[0022] More preferably, the volume ratio of petroleum ether to ethyl acetate in the eluent is 10:1 to 3:1.

[0023] In a preferred embodiment of the present invention, in step (1), the ratio of aryl-containing 1,3-enyne, aryl bromide, copper salt, palladium, ligand, diboron reagent, and base is 0.45 mmol: 0.3 mmol: 0.018 mmol: 0.024 mmol: 0.033 mmol, 0.6 mmol, and 0.6 mmol: 3 mL.

[0024] In a preferred embodiment of the present invention, the reaction time in step (1) is 96 hours.

[0025] A method for synthesizing axially chiral alkenylboronic esters containing carboxylic acid esters includes the following steps:

[0026] (1) Add aryl-containing 1,3-enyne, aryl bromide containing carboxylic acid ester, copper salt, palladium, and ligand to a pressure-resistant sealed reaction vessel. Add diboron reagent and base in a glove box, remove air, fill with argon, add organic solvent, and stir the reaction at 15°C for 72 h.

[0027] (2) Take the material obtained in step (1) out of the pressure-resistant sealed reaction vessel, cool it to room temperature, add ethyl acetate and elute it with a short silica gel column to obtain the crude product, and extract the organic phase three times with water at 60°C; (3) evaporate the organic solvent in the organic phase obtained in step (2), purify it with a silica gel column, and then wash it with an eluent to obtain the axially chiral alkenyl borate containing carboxylic acid ester.

[0028] In a preferred embodiment of the present invention, the aryl-containing 1,3-enyne is one of the following: alkyl-substituted aryl-containing 1,3-enyne, aryl-containing 1,3-enyne without benzene ring substitution, aryl-containing 1,3-enyne with benzene ring substitution, and aryl-containing 1,3-enyne with polysubstituted benzene ring.

[0029] In a preferred embodiment of the present invention, the aryl bromide containing a carboxylic acid ester is an aryl bromide containing a carboxylic acid ester with no substituted benzene ring, an aryl bromide containing a carboxylic acid ester with a monosubstituted benzene ring, or an aryl bromide containing a carboxylic acid ester with no substituted naphthalene ring.

[0030] In a preferred embodiment of the present invention, the copper salt is one of 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ethylene copper salt and 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ethylene copper salt.

[0031] A further preferred copper salt is 1,3-bis(2,6-diisopropylphenyl)imidazol-2-methylene copper salt.

[0032] In a preferred embodiment of the present invention, the palladium catalyst is palladium acetate or palladium bromide.

[0033] A further preferred palladium catalyst is palladium acetate.

[0034] In a preferred embodiment of the present invention, the ligand is one of (R)-4-(anthra-9-yl)-3-(tert-butyl)-2,3-dihydrobenzo[d][1,3]oxophosphacyclopentadiene, (S)-3-(tert-butyl)-4-(2,6-dimethoxy-3,5-dimethylphenyl)-2,3-dihydrobenzo[d][1,3]oxophosphacyclopentadiene, and (3aS,8aR)-2-(m-methyl)-3a,8a-dihydro-8H-indene[1,2-d]dioxazole.

[0035] A further preferred ligand is one of ((S)-3-(tert-butyl)-4-(2,6-dimethoxy-3,5-dimethylphenyl)-2,3-dihydrobenzo[d][1,3]oxophosphanecyclopentadiene.

[0036] In a preferred embodiment of the present invention, the diboron reagent is pinacol diborate.

[0037] In a preferred embodiment of the present invention, the alkali is one of sodium tert-amyl alcohol or sodium tert-butoxide.

[0038] A further preferred alkali is sodium tert-amyl alcohol.

[0039] In a preferred embodiment of the present invention, the organic solvent is one of mesitylene, trifluorotoluene, and methyl cyclopentyl ether.

[0040] A further preferred organic solvent is trifluorotoluene: methyl cyclopentyl ether at a ratio of 1:1.

[0041] In a preferred embodiment of the present invention, the eluent is a mixed solution of petroleum ether and ethyl acetate.

[0042] More preferably, the volume ratio of petroleum ether to ethyl acetate in the eluent is 10:1 to 3:1.

[0043] In a preferred embodiment of the present invention, in step (1), the ratio of aryl-containing 1,3-enyne, aryl carboxylic acid bromide, copper salt, palladium, ligand, diboron reagent, and base is 0.3 mmol: 0.3 mmol: 0.012 mmol: 0.016 mmol: 0.022 mmol, 0.4 mmol, and 0.4 mmol: 2 mL.

[0044] In a preferred embodiment of the present invention, the reaction time in step (1) is 72 hours.

[0045] The beneficial effects of this invention are:

[0046] 1. This invention enables the synthesis of highly selective axially chiral alkenyl borate esters containing phosphine or carboxylic acid esters through the arylation reaction of aryl-containing 1,3-enynes, phosphorus-containing or carboxylic acid ester-containing aryl bromides, with phosphine cyclopentadiene as a ligand, and diboron reagent under copper-palladium dual catalysis.

[0047] 2. In line with the concept of green chemistry: The synthesis method of this invention uses copper-palladium dual catalysis, which is environmentally friendly.

[0048] 3. Simple operation: The synthesis method of the present invention is simple to operate and can obtain axial chiral alkenyl borate in one step.

[0049] 4. The phosphine-containing axially chiral alkenylboronic ester synthesized in this invention can be effectively converted into axially chiral phosphine-olefins, which can be used as ligands in palladium-catalyzed asymmetric allylation reactions. Detailed Implementation

[0050] To make the above-mentioned features and advantages of the present invention more apparent and understandable, specific embodiments are described below in detail. Unless otherwise specified, the methods of the present invention are conventional methods in the art.

[0051] Example 1:

[0052]

[0053] Add 0.45 mmol (1E)-1-phenyl-1-octen-3-yne, 0.30 mmol of aryl bromide containing phosphine oxide (e.g., 1-bromonaphthol-2-diphenylphosphine), 0.018 mmol of 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylcopper salt (CAS No. 873779-78-3), 0.024 mmol of palladium acetate, and 0.033 mmol (R)-4-(anthracite-9-yl)-3-(tert-butyl)-2,3-dihydrobenzo[d][1,3]oxophosphazenecyclopentadiene (ligand L1) to a 10 ml Young's tube containing a magnetic spool. Place the sample in a nitrogen-filled glove box, add 0.6 mmol sodium tert-amyl alcohol, 0.6 mmol pinacol diborate, and 3 ml of ultra-dry trimethylbenzene. Then seal the tube with a Teflon-lined screw cap and remove it from the glove box. The reaction mixture was then stirred at 40°C for 96 h until the reaction was complete. Ethyl acetate was added, and the crude product was eluted using a short silica gel column. The organic phase was extracted three times with water at 60°C, the organic solvent was evaporated, and the product was purified by silica gel column chromatography. The final product was obtained by elution with petroleum ether:ethyl acetate = 10:1 (v / v). The yield was 84%, and the er value was 99.5:0.5.

[0054] (1E)-1-phenyl-1-octene-3-yne is a publicly reported raw material. Reference: Guo, Z., Wen, H., Liu, G. & Huang, Z. Iron-catalyzed regio-and stereoselective hydrosilylation of 1,3-enynesto access 1,3-dienylsilanes. Org. Lett. 23, 2375-2379 (2021).

[0055] 1-Bromonaphthol-2-diphenylphosphine is a publicly reported raw material. Reference: Feng, J., Li, B., He, Y. & Gu, Z. Enantioselective synthesis of atropisomeric vinyl arene compounds by palladium catalysis: a carbene strategy. Angew. Chem. Int. Ed. 55, 2186-2190 (2016).

[0056] The universality of the substrates was studied under the standard conditions of this invention to demonstrate that the technical solution of this invention has good functional group compatibility. The substrate range is as follows:

[0057]

[0058] The corresponding products are as follows:

[0059]

[0060] Example 2:

[0061]

[0062] In a 10 ml Young's tube equipped with a magnetic inlet, add 0.45 mmol of 1,3-enyne (using (1E)-1,6-diphenyl-1-hexen-3-yne as an example), 0.30 mmol of 1-bromonaphthol-2-diphenylphosphine, 0.018 mmol of 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ethylene copper salt, 0.024 mmol of palladium acetate, and 0.033 mmol of (R)-4-(anthracite-9-yl)-3-(tert-butyl)-2,3-dihydrobenzo[d][1,3]oxophosphazenecyclopentadiene. Place the sample in a nitrogen-filled glove box, add 0.6 mmol of sodium tert-amyl alcohol, 0.6 mmol of pinacol diborate, and 3 ml of ultra-dry trimethylbenzene. Then seal the tube with a Teflon-lined screw cap and remove it from the glove box. The reaction mixture is then stirred at 40 °C for 96 h until the reaction is complete. The crude product was obtained by elution with ethyl acetate through a short silica gel column. The organic phase was extracted three times with water at 60°C, the organic solvent was evaporated, and the product was purified by silica gel column chromatography. The final product was obtained by elution with petroleum ether:ethyl acetate = 10:1 (v / v). The yield was 81%, and the er value was 99:1.

[0063] The universality of the substrates was studied under the standard conditions of this invention to demonstrate that the technical solution of this invention has good functional group compatibility. The substrate scope is as follows:

[0064]

[0065] The corresponding products are as follows:

[0066]

[0067] Example 3:

[0068]

[0069] Add 0.45 mmol of 1,3-enyne (using (1E)-1,6-diphenyl-1-hexen-3-yne as an example), 0.30 mmol of 1-bromo-2-naphthyl oxetane ester, 0.018 mmol of 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylcopper salt, 0.024 mmol of palladium acetate, and 0.033 mmol of (S)-3-(tert-butyl)-4-(2,6-dimethoxy-3,5-dimethylphenyl)-2,3-dihydrobenzo[d][1,3]oxophosphazenecyclopentadiene (ligand L2) to a 10 ml Young's tube containing a magnetic spool. Place the sample in a nitrogen-filled glove box, add 0.6 mmol of sodium tert-amyl alcohol, 0.6 mmol of pinacol diborate, and 3 ml of ultra-dry trimethylbenzene. Then seal the tube with a Teflon-lined screw cap and remove it from the glove box. The reaction mixture was then stirred at 15°C for 72 h until the reaction was complete. Ethyl acetate was added, and the crude product was eluted using a short silica gel column. The organic phase was extracted three times with water at 60°C, the organic solvent was evaporated, and the product was purified by silica gel column chromatography. The final product was obtained by elution with an eluent (petroleum ether:ethyl acetate = 10:1, v / v) to give the target product. The yield was 89%, and the ER value was 95.5:4.5.

[0070] The universality of the substrates was studied under the standard conditions of this invention to demonstrate that the technical solution of this invention has good functional group compatibility. The substrate scope is as follows:

[0071]

[0072] The corresponding products are as follows:

[0073]

[0074] Example 4:

[0075]

[0076] In a 10 mL Young's tube equipped with a magnetic inlet, add 0.45 mmol of (1E)-1-phenyl-1-octen-3-yne, 0.30 mmol of 1-bromo-2-naphthyl oxetane ester, 0.018 mmol of 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-yl copper salt, 0.024 mmol of palladium acetate, and 0.033 mmol of (S)-3-(tert-butyl)-4-(2,6-dimethoxy-3,5-dimethylphenyl)-2,3-dihydrobenzo[d][1,3]oxophosphazenecyclopentadiene (ligand L2). Place the sample in a nitrogen-filled glove box, add 0.6 mmol of sodium tert-amyl alcohol, 0.6 mmol of pinacol diborate, and 3 mL of ultra-dry trimethylbenzene. Seal the tube with a Teflon-lined screw cap and remove it from the glove box. Then stir the reaction mixture at 15 °C for 72 h until the reaction is complete. Ethyl acetate was added and eluted through a short silica gel column to obtain the crude product. The organic phase was extracted three times with water at 60°C, the organic solvent was evaporated, and the product was purified by silica gel column chromatography. The crude product was then eluted with petroleum ether:ethyl acetate = 10:1 (v / v) to obtain the target product. The yield was 89%, and the ER value was 95.5:4.5.

[0077] The universality of the substrates was studied under the standard conditions of this invention to demonstrate that the technical solution of this invention has good functional group compatibility. The substrate scope is as follows:

[0078]

[0079] The corresponding products are as follows:

[0080]

[0081] The references to some of the raw materials used in the examples are as follows: 1. Feng, J., Li, B., He, Y. & Gu, Z. Enantioselective synthesis of atropisomeric vinyl arene compounds by palladium catalysis: a carbene strategy. Angew. Chem. Int. Ed. 55, 2186-2190 (2016).

[0082] 2Ji,W.,Wu,H.-H.&Zhang,J.Axially chiral biaryl monophosphine oxidesenabled by palladium / wj-phos-catalyzed asymmetric suzuki–miyaura cross-coupling.ACS Catal.10,1548-1554(2020).

[0083] 3Zhu,Y.et al.Copper(I)-catalyzed synthesis of 1,3-enynes via couplingbetween vinyl halides and alkynes or domino coupling ofvinylhalides.Org.Biomol.Chem.9,7309-7312(2011).

[0084] 4Wu,Y.,Huang,M.,Mi,X.&Feng,Y.Discovery ofa novel palladium catalystfor the preparation ofenynes with a copper-and ligand-free sonogashirareaction.Synlett23,1257-1261(2012).

[0085] 5Zhang,H.&Larock,R.C.Synthesis ofannulatedγ-carbolines andheteropolycycles by the palladium-catalyzed intramolecular annulationofalkynes.J.Org.Chem.68,5132-5138(2003).

[0086] 6Wang,X.,Liu,Y.&Martin,R.Ni-catalyzed divergent cyclization / carboxylation ofunactivatedprimary and secondary alkyl halides withCO2.J.Am.Chem.Soc.137,6476-6479(2015)

[0087] 7Guo,Z.,Wen,H.,Liu,G.&Huang,Z.Iron-catalyzed regio-andstereoselective hydrosilylation of 1,3-enynes to access 1,3-dienylsilanes.Org.Lett.23,2375-2379(2021).

[0088] Substrates 1a, 1b, 1c, 1d, 1e, and 1h are reported in reference 1.

[0089] Substrate 1f, 1g, 1i are reported in reference 2;

[0090] Substrate 2a is reported in reference 3;

[0091] Substrate 2c is reported in reference 4;

[0092] Substrate 2b is reported in reference 5;

[0093] See reference 6 for substrate 2d;

[0094] The substrate content was 2 g and 2 j (see reference 7).

[0095] The preparation methods of substrates 2e-2f, 2h-2i, and 2m-2o are as follows:

[0096]

[0097] In a 100 mL round-bottom flask, add 0.08 mmol tetra(triphenylphosphine palladium), 0.55 mmol cuprous iodide, 5.0 mmol aryl alkenyl bromide, and 6.0 mmol 1-hexyne, dissolved in 25 mL diethylamine. Stir at room temperature for 12 h until the reaction is complete. Extract the organic phase three times with water and ethyl acetate, dry with anhydrous sodium sulfate, evaporate the organic solvent to dryness, purify by silica gel column chromatography, and elute with petroleum ether:ethyl acetate 30:1 to 10:1 to obtain the target product.

[0098] The preparation method of substrate 1j-1m is as follows:

[0099]

[0100] In a 50 mL round-bottom flask, add 4.0 mmol of 1-bromo-2-naphthalene, 4.8 mmol of N,N'-dicyclohexylcarboimide, and 0.8 mmol of 4-methylaminopyridine, dissolve in 10 mL of dichloromethane, and then add 4.4 mmol of alcohol or phenol (for example, p-methylphenol is added in 1 J). Stir at room temperature for 12 h until the reaction is complete. Filter the reaction solution through a short silica gel column, wash with dichloromethane, evaporate to dryness, purify with silica gel column chromatography, and then elute with an eluent (petroleum ether:ethyl acetate 30:1 to 10:1) to obtain the target product.

[0101] Application Example 1:

[0102]

[0103] 0.1 mmol of compound 1 was added to a 10 mL Young's tube, followed by 0.2 mmol of bis(p-nitrophenyl) phosphate (CAS No. 645-15-8), 1 mL of tetrahydrofuran solvent, and 1 mmol of phenylsilane. The reaction was carried out under argon protection at 80 °C for 8 h. After the reaction was completed, the solvent was evaporated to dryness, and the crude product was eluted by silica gel chromatography (petroleum ether:ethyl acetate = 50:1 v / v) to give product 32 in 71% yield with an ER value of 99.5:0.5.

[0104] Product 32 can be used as a ligand in palladium-catalyzed asymmetric allylation reactions.

[0105] In a 10 mL Young's tube, 0.004 mmol of ligand 32, 0.002 mmol of allyl palladium(II) chloride dimer (CAS No. 12012-95-2), and 0.016 mmol of lithium acetate were added in diethyl ether. Then, 0.4 mmol of N,O-bis(trimethylsilylacetamide) (CAS No. 10416-59-8) and 0.2 mmol of 1,3-diphenylallyl acetate (CAS No. 73930-97-9) were added. After stirring at room temperature for 30 minutes, 0.3 mmol of dimethyl malonate was added at -20 °C, and the mixture was stirred for 10 h. After the reaction was complete, the solvent was evaporated to dryness, and the crude product was eluted by silica gel chromatography (petroleum ether:ethyl acetate = 10:1 v / v) to obtain product 33 in 90% yield with an er value of 71:29. This reaction demonstrates that the prepared ligand has the potential for application in palladium-catalyzed asymmetric allylation reactions.

[0106] The specific NMR data for the above substrates are as follows:

[0107] 1j

[0108] 1 H NMR (500MHz, CDCl3): δ8.47–8.44(m,1H),7.85–7.80(m,2H),7.69(d,J=8.5Hz,1H),7.6 6–7.57(m,2H),7.40(d,J=8.1Hz,2H),7.22(d,J=7.8Hz,2H),5.41(s,2H),2.38(s,3H).

[0109] 13 C NMR (126MHz, CDCl3): δ167.37,138.43,135.29,132.59,132.42,131.33,129.43,1 28.78,128.68,128.30,128.24,128.22,127.92,125.98,122.88,67.70,21.38.1k

[0110] 1 H NMR(500 MHz,CDCl3):δ8.46–8.43(m,1H),7.85–7.80(m,2H),7.67(d,J=8.4Hz,1H),7.66–7.62(m,1H),7.61–7.57(m,1H),7.01–6.96(m,2H),6.82(d,J=7.9 Hz,1H),5.98(s,2H),5.34(s,2H).

[0111] 13 C NMR(126 MHz,CDCl3):δ167.34,147.98,147.94,135.31,132.43,131.27,129.32,128.68,128.32,128.28,128.25,127.96,125.93,122.87,122.78,109.44,108.43,101.34,67.74.

[0112] 1l

[0113] 1 H NMR(500 MHz,CDCl3):δ8.49–8.40(m,1H),7.88–7.78(m,2H),7.67–7.63(m,2H),7.61–7.58(m,2H),7.44(t,J=1.7 Hz,1H),6.56(dd,J=0.8,2.0 Hz,1H),5.32(s,2H).

[0114] 13 C NMR(126 MHz,CDCl3):δ167.37,143.63,142.05,135.30,132.40,131.23,128.67,128.30,128.28,128.26,127.96,125.88,122.83,120.17,110.88,59.17.

[0115] 1m

[0116] 1H NMR(500 MHz,CDCl3):δ8.30(d,J=8.3 Hz,1H),7.62(dd,J=5.5,8.0 Hz,2H),7.55(d,J=8.5 Hz,1H),7.48–7.44(m,1H),7.42–7.38(m,1H),7.35(dd,J=1.1,2.9 Hz,1H),7.24(dd,J=2.9,5.0 Hz,1H),7.15(dd,J=1.3,5.0 Hz,1H),5.39(s,2H).

[0117] 13 C NMR(126 MHz,CDCl3):δ166.85,136.17,134.87,131.95,130.80,128.22,127.97,127.93,127.65,127.62,126.21,125.58,124.64,122.57,62.38.

[0118] 2e

[0119] 1 H NMR(500 MHz,CDCl3):δ7.49–7.39(m,1H),7.18(dt,J=3.6,7.8 Hz,3H),7.14(d,J=16.3 Hz,1H),6.10(dt,J=2.3,16.1 Hz,1H),2.41(td,J=2.2,7.1 Hz,2H),2.38(s,3H),1.63–1.57(m,2H),1.53–1.45(m,2H),1.08–0.88(m,3H).

[0120] 13 C NMR(126 MHz,CDCl3):δ137.82,135.65,130.54,128.21,126.26,124.92,110.00,92.71,80.14,31.01,22.18,19.90,19.47,13.77.

[0121] 2f

[0122] 1H NMR(500 MHz,CDCl3):δ7.18–7.14(m,1H),7.14–7.12(m,2H),7.07–6.98(m,1H),6.81(d,J=16.2 Hz,1H),6.12(dt,J=2.3,16.2 Hz,1H),2.35(td,J=2.1,7.0 Hz,2H),2.30(s,3H),1.58–1.49(m,2H),1.48–1.39(m,2H),0.92(t,J=7.3Hz,3H).

[0123] 13 C NMR(126 MHz,CDCl3):δ140.10,138.16,136.61,129.06,128.56,126.79,123.23,108.76,92.83,79.95,30.98,22.10,21.37,19.41,13.70.

[0124] 2h

[0125] 1 H NMR(500 MHz,CDCl3):δ7.26(s,4H),6.79(d,J=16.2 Hz,1H),6.12(dt,J=2.3,16.2 Hz,1H),2.36(td,J=2.3,7.0 Hz,2H),1.58–1.51(m,2H),1.49–1.40(m,2H),0.93(t,J=7.3 Hz,3H).

[0126] 13 C NMR(126 MHz,CDCl3):δ138.65,135.18,133.92,128.92,127.27,109.73,93.79,79.60,30.93,22.13,19.45,13.73.

[0127] 2i

[0128] 1 H NMR(500 MHz,CDCl3):δ7.38–7.35(m,3H),7.16(d,J=7.9 Hz,2H),6.84(d,J=16.1 Hz,1H),6.14(dt,J=2.2,16.3 Hz,1H),2.39(td,J=2.2,7.1 Hz,2H),1.62–1.52(m,2H),1.50–1.45(m,2H),0.96(t,J=7.3 Hz,3H).

[0129] 13 C NMR(126 MHz,CDCl3):δ149.06,138.37,135.49,127.37,121.21,120.62(q,J=257.2 Hz),110.20,93.87,79.54,30.97,22.16,19.45,13.67.

[0130] 2k

[0131] 1 H NMR(500 MHz,CDCl3):δ7.37–7.34(m,2H),7.33–7.28(m,2H),7.27–7.23(m,1H),6.87(d,J=16.2 Hz,1H),6.14(dt,J=2.2,16.2 Hz,1H),3.22(t,J=6.9,6.9 Hz,2H),2.40(td,J=2.2,6.9 Hz,2H),2.02–1.92(m,2H),1.73–1.62(m,2H). 13 C NMR(126 MHz,CDCl3):δ140.46,136.56,128.78,128.44,126.19,108.69,91.86,80.51,32.59,29.55,18.76,6.36.

[0132] 2l

[0133] 1 H NMR(500 MHz,CDCl3):δ7.96(d,J=1.1 Hz,1H),7.94(d,J=1.4 Hz,1H),7.51–7.47(m,1H),7.40(t,J=7.7 Hz,2H),7.32–7.30(m,2H),7.27–7.24(m,2H),7.22–7.18(m,1H),6.84(d,J=16.2 Hz,1H),6.13(dt,J=2.2,16.2 Hz,1H),3.08(t,J=7.2 Hz,2H),2.48(td,J=2.3,6.9 Hz,2H),1.98(p,J=7.1 Hz,2H).

[0134] 13C NMR(126 MHz,CDCl3):δ199.35,140.17,136.80,136.29,132.89,128.56,128.46,128.21,127.92,125.96,108.58,91.92,80.61,37.11,23.04,19.07.

[0135] 2m

[0136] 1 H NMR(500 MHz,CDCl3):δ7.61–7.54(m,2H),7.51(d,J=8.3 Hz,2H),7.44–7.36(m,4H),7.35–7.27(m,1H),6.88(d,J=16.2Hz,1H),6.18(dt,J=2.1,16.3Hz,1H),2.45–2.27(m,2H),1.60–1.50(m,2H),1.49–1.39(m,2H),0.93(t,J=7.3Hz,3H).

[0137] 13 C NMR(126MHz,CDCl3):δ140.98,140.59,139.57,135.72,128.90,127.50,127.38,126.99,126.58,109.04,93.41,79.99,31.00,22.14,19.50,13.76.

[0138] 2n

[0139] 1 H NMR(500MHz,CDCl3):δ7.32–7.28(m,3H),7.28–7.26(m,1H),7.11–7.05(m,1H),7.01–6.99(m,1H),6.99–6.97(m,1H),6.94–6.89(m,2H),6.81(d,J=16.2Hz,1H),6.05(dt,J=16.1,2.2Hz,1H),2.35(td,J=7.0,2.3Hz,2H),1.57–1.49(m,2H),1.48–1.39(m,2H),0.92(t,J=7.3Hz,3H).

[0140] 13C NMR (126MHz, CDCl3): δ157.51,156.89,139.14,131.79,129.83,127.48,1 23.55,119.16,118.78,107.95,92.73,79.93,30.94,22.07,19.39,13.70.

[0141] HRMS(EI): calc'd for C 20 H 20 O 276.1514, found 276.1507.

[0142] 2o

[0143] 1 H NMR (500MHz, CDCl3): δ8.17(d,J=7.9Hz,1H),7.88(dd,J=2.1,7.3Hz,1H),7.83(d,J=8.2Hz,1H),7.73(d,J=16.0Hz,1H),7.66(d,J=7.2Hz,1H),7.5 8–7.50(m,3H),7.47(m,1H),6.29(dt,J=2.3,15.8Hz,1H),2.48(td,J=2.3 ,7.1Hz,2H),1.69–1.63(m,2H),1.60–1.51(m,2H),1.03(t,J=7.3Hz,3H).

[0144] 13 C NMR (126MHz, CDCl3): δ137.15,134.20,133.75,130.94,128.70,128.65,126.35,1 26.01,125.68,123.76,123.32,111.76,92.97,80.16,31.01,22.20,19.50,13.80.

[0145] The specific NMR data for the above products are as follows: 1

[0147] 1H NMR(500MHz,CDCl3):δ7.92(d,J=8.5Hz,1H),7.81–7.76(m,2H),7.75(dd,J=1.4,4.7Hz,2H),7.74–7.69(m,2H),7.53–7.45(m,2H),7.44–7.36(m,2H),7.36–7.29(m,3H),7.28–7.23(m,2H),7.17(dd,J=4.2,11.8Hz,3H),7.13–7.09(m,1H),7.10–7.06(m,2H),5.81(d,J=16.1Hz,1H),2.38–2.23(m,2H),1.73–1.59(m,1H),1.57–1.49(m,1H),1.49–1.40(m,2H),0.99(t,J=7.2Hz,3H),0.84(s,6H),0.60(s,6H).

[0148] 13 C NMR(126MHz,CDCl3):δ146.42,146.35,144.83,144.79,137.57,135.16,134.68,134.55,134.54,134.43,134.34,134.04,133.94,133.86,133.67,132.89,132.81,132.32,132.25,131.16,131.14,131.06,131.04,128.95,128.85,128.27,128.16,127.88,127.79,127.67,127.57,127.50,127.48,127.40,127.33,127.26,126.78,126.48,126.27,126.17,82.42,32.34,30.69,24.44,23.96,23.25,14.19.(Due to C-P coupling and thecomplexity ofthe spectrum,doublets in the aromatic region cannot be assignedand they are listed as singlets).

[0149] 31 P NMR(202 MHz,CDCl3):δ28.90.

[0150] 11 B NMR(160 MHz,CDCl3):δ28.12. 2

[0152] 1 H NMR(500 MHz,CDCl3):δ7.94(d,J=8.5 Hz,1H),7.91–7.81(m,6H),7.67–7.62(m,1H),7.61–7.58(m,4H),7.54–7.51(m,3H),7.49–7.45(m,4H),7.45–7.41(m,3H),7.40–7.35(m,2H),7.22–7.16(m,3H),7.13(dd,J=6.9,13.2 Hz,3H),5.85(d,J=16.0 Hz,1H),2.41–2.26(m,2H),1.73–1.62(m,1H),1.61–1.50(m,1H),1.50–1.40(m,2H),0.99(t,J=7.3Hz,3H),0.90(s,6H),0.67(s,6H).

[0153] 13 C NMR(126 MHz,CDCl3):δ146.54,146.47,144.81,144.77,144.04,143.93,140.51,140.38,137.70,134.71,134.17,134.08,133.90,133.46,133.38,133.03,132.94,132.86,132.51,129.01,128.90,128.47,128.14,128.04,127.96,127.59,127.50,127.39,126.82,126.73,126.63,126.57,126.48,126.38,82.55,32.45,30.84,24.54,24.16,23.32,14.22.(Due to C-P coupling and the complexity ofthe spectrum,doubletsin the aromatic region cannot be assigned and they are listed as singlets).

[0154] 31 P NMR(202 MHz,CDCl3):δ28.39.

[0155] 11 B NMR(160 MHz,CDCl3):δ28.96. 3

[0157] 1 H NMR(500 MHz,CDCl3):δ7.91(d,J=8.6 Hz,1H),7.82–7.77(m,2H),7.76–7.66(m,4H),7.53–7.49(m,1H),7.46(dd,J=8.6,12.0 Hz,1H),7.43–7.39(m,1H),7.22(t,J=7.3 Hz,2H),7.18–7.13(m,2H),7.09(d,J=7.2 Hz,2H),7.02(td,J=2.0,8.8 Hz,2H),6.96(td,J=2.0,8.8 Hz,2H),5.77(d,J=16.1 Hz,1H),2.36–2.25(m,2H),1.69–1.60(m,1H),1.56–1.41(m,3H),0.99(t,J=7.2 Hz,3H),0.84(s,6H),0.60(s,6H).

[0158] 13 C NMR(126 MHz,CDCl3):δ165.79,165.76,165.73,163.78,163.75,163.73,146.43,146.37,144.66,144.62,137.41,135.41,135.35,135.33,135.26,134.81,134.73,134.65,134.05,133.93,131.08,130.62,130.20,129.78,128.67,128.57,128.50,128.15,127.90,127.82,127.72,127.61,127.37,127.05,126.76,126.61,126.51,115.44,115.33,115.27,115.16,115.05,114.98,114.88,82.59,32.38,30.78,24.50,24.03,23.31,14.21.(Due to C-P and C-F coupling and the complexity ofthe spectrum,doublets inthe aromatic region cannot be assigned and they are listed as singlets).

[0159] 31P NMR(202 MHz,CDCl3):δ27.52.

[0160] 11 B NMR(160 MHz,CDCl3):δ31.91. 4

[0162] 1 H NMR(500 MHz,CDCl3):δ7.91(d,J=8.5 Hz,1H),7.79(d,J=8.0 Hz,1H),7.77(dd,J=2.1,8.7 Hz,1H),7.62(d,J=12.1 Hz,1H),7.57(d,J=12.3 Hz,1H),7.53(dd,J=8.6,11.8 Hz,1H),7.50–7.43(m,3H),7.42–7.36(m,1H),7.25–7.12(m,8H),7.11–7.07(m,2H),5.78(d,J=16.0 Hz,1H),2.32–2.28(m,2H),2.27(s,3H),2.16(s,3H),1.69–1.59(m,1H),1.57–1.39(m,3H),1.00(t,J=7.2 Hz,3H),0.84(s,6H),0.62(s,6H).

[0163] 13C NMR(126 MHz,CDCl3):δ146.31,146.24,144.76,144.72,137.91,137.82,137.69,137.48,137.38,135.12,134.59,134.57,134.30,134.16,134.06,133.77,133.64,133.29,133.22,132.99,132.92,132.01,131.99,131.89,131.87,130.13,130.05,129.60,129.49,129.41,129.11,129.01,128.55,128.32,128.18,127.72,127.59,127.53,127.49,127.43,127.40,126.80,126.42,126.26,126.16,82.43,32.44,30.67,24.46,24.13,23.32,21.53,21.35,14.23.(Due to C-P coupling and the complexity of thespectrum,doublets in the aromatic region cannot be assigned and they arelisted as singlets).

[0164] 31 P NMR(202 MHz,CDCl3):δ29.02.

[0165] 11 B NMR(128 MHz,CDCl3):δ30.62. 5

[0167] 1H NMR(500 MHz,CDCl3):δ7.90(d,J=8.5 Hz,1H),7.83–7.72(m,2H),7.56–7.45(m,2H),7.41–7.37(m,1H),7.36–7.30(m,2H),7.30–7.26(m,1H),7.26–7.22(m,2H),7.20–7.16(m,3H),7.15–7.09(m,4H),6.98–6.93(m,1H),6.84(dd,J=2.6,8.2 Hz,1H),5.80(d,J=16.0 Hz,1H),3.65(s,3H),3.59(s,3H),2.32(t,J=7.9 Hz,2H),1.69–1.59(m,1H),1.57–1.48(m,1H),1.48–1.40(m,2H),0.99(t,J=7.2 Hz,3H),0.83(s,6H),0.62(s,6H).

[0168] 13 C NMR(126 MHz,CDCl3):δ159.29,159.17,159.08,158.96,146.38,146.31,144.44,144.40,137.63,136.18,135.96,135.37,135.15,134.60,134.07,133.97,133.51,128.95,128.88,128.76,128.31,128.22,128.06,127.49,127.41,127.40,126.75,126.45,126.35,126.25,125.26,125.18,124.61,124.53,117.84,117.75,117.33,117.31,117.28,117.26,117.20,117.12,82.48,55.24,55.16,32.36,30.67,24.37,24.05,23.26,14.21.(Due to C-P coupling and the complexity ofthe spectrum,doublets in thearomatic region cannot be assigned and they are listed as singlets). 31 P NMR(202 MHz,CDCl3):δ28.94.

[0169] 11B NMR(128 MHz,CDCl3):δ30.15. 6

[0171] 1 H NMR(500 MHz,CDCl3):δ7.93(d,J=8.5 Hz,1H),7.89–7.71(m,2H),7.60–7.39(m,7H),7.37–7.30(m,1H),7.28–7.24(m,1H),7.23–7.17(m,3H),7.17–7.12(m,2H),7.12–7.08(m,2H),7.04(td,J=2.6,8.5 Hz,1H),5.78(d,J=16.0 Hz,1H),2.41–2.25(m,2H),1.71–1.61(m,1H),1.58–1.49(m,1H),1.49–1.41(m,2H),1.00(t,J=7.2 Hz,3H),0.84(s,6H),0.60(s,6H).

[0172] 13C NMR(126 MHz,CDCl3):δ163.45,163.32,163.18,161.47,161.33,161.19,146.93,146.86,144.21,144.17,137.56,137.52,137.40,137.12,137.08,136.74,136.70,136.31,136.27,134.84,134.82,134.03,133.95,130.09,130.03,129.98,129.92,129.67,129.61,129.56,129.50,128.55,128.49,128.42,128.01,127.97,127.67,127.65,127.38,127.02,126.87,126.78,126.66,126.55,126.17,119.86,119.78,119.69,119.60,119.20,119.11,119.02,118.94,118.73,118.62,118.57,118.46,82.70,32.32,30.72,24.44,23.97,23.34,14.21.(Due to C-P and C-F coupling,and the complexity ofthespectrum,doublets in the aromatic region cannot be assigned and they arelisted as singlets).

[0173] 31 P NMR(202 MHz,CDCl3):δ26.92.

[0174] 11 B NMR(128 MHz,CDCl3):δ29.79.

[0175] 7 1H NMR(500 MHz,CDCl3):δ7.94(d,J=8.6 Hz,1H),7.82(d,J=8.2 Hz,2H),7.74(dt,J=1.7,1.7,7.2 Hz,1H),7.72(dt,J=1.7,7.5 Hz,1H),7.66–7.60(m,1H),7.60–7.55(m,1H),7.55–7.50(m,1H),7.49–7.40(m,3H),7.34–7.31(m,1H),7.28(td,J=3.3,7.8 Hz,1H),7.24–7.19(m,3H),7.19–7.11(m,4H),5.81(d,J=16.1 Hz,1H),2.35–2.22(m,2H),1.73–1.60(m,1H),1.59–1.49(m,1H),1.49–1.42(m,2H),1.01(t,J=7.2 Hz,3H),0.85(s,6H),0.62(s,6H).

[0176] 13 C NMR(126 MHz,CDCl3):δ146.76,146.69,143.94,143.90,137.30,137.05,136.79,136.24,135.99,134.87,134.85,134.75,134.63,134.39,134.25,134.01,133.91,132.61,132.52,131.95,131.86,131.67,131.65,131.61,131.59,130.94,130.87,130.40,130.33,129.51,129.41,129.17,129.07,128.50,128.43,128.41,127.98,127.83,127.73,127.67,127.36,126.92,126.83,126.78,126.67,126.07,82.67,32.35,30.65,24.42,24.14,23.33,14.19,136.54–136.44(m).(Due to C-P coupling and the complexity ofthe spectrum,doublets in the aromatic region cannot be assigned and they arelisted as singlets).

[0177] 31P NMR(202 MHz,CDCl3):δ26.74.

[0178] 11 B NMR(128 MHz,CDCl3):δ30.79. 8

[0180] 1 H NMR(500 MHz,CDCl3):δ7.93(d,J=8.5 Hz,1H),7.80(d,J=8.1 Hz,1H),7.78(dd,J=2.0,8.7 Hz,1H),7.54(dd,J=8.6,11.8 Hz,1H),7.51–7.46(m,1H),7.42–7.37(m,1H),7.34(t,J=12.0 Hz,4H),7.24–7.16(m,3H),7.15–7.08(m,3H),7.06(s,1H),6.91(s,1H),5.77(d,J=16.0 Hz,1H),2.33(t,J=7.9 Hz,2H),2.26(s,6H),2.14(s,6H),1.71–1.60(m,1H),1.59–1.52(m,1H),1.52–1.44(m,2H),1.02(t,J=7.3 Hz,3H),0.84(s,6H),0.65(s,6H).

[0181] 13C NMR(126 MHz,CDCl3):δ146.26,146.19,144.37,144.34,137.66,137.33,137.27,137.23,137.17,135.08,134.51,134.49,134.26,134.19,134.09,133.55,133.43,132.91,132.82,130.29,130.22,130.06,129.98,129.11,129.01,128.66,128.21,127.84,127.41,127.36,127.29,126.67,126.26,126.15,126.05,82.32,32.44,30.52,24.37,24.27,23.27,21.39,21.23,14.20.(Due to C-P coupling and the complexity of thespectrum,doublets in the aromatic region cannot be assigned and they arelisted as singlets).

[0182] 31 P NMR(202 MHz,CDCl3):δ28.79.

[0183] 11 B NMR(128 MHz,CDCl3):δ30.19. 9

[0185] 1H NMR(500 MHz,CDCl3):δ7.91(d,J=8.5 Hz,1H),7.80(d,J=8.0 Hz,1H),7.76(dd,J=1.9,8.6 Hz,1H),7.68(d,J=1.7 Hz,1H),7.66(d,J=1.7 Hz,1H),7.59(d,J=1.7Hz,1H),7.57(d,J=1.7 Hz,1H),7.54(s,1H),7.49–7.43(m,2H),7.41–7.34(m,2H),7.20(d,J=16.0 Hz,1H),7.13(t,J=7.3 Hz,2H),7.07(t,J=7.2 Hz,1H),6.98(d,J=7.2 Hz,2H),5.67(d,J=16.0 Hz,1H),2.54–2.47(m,1H),2.46–2.37(m,1H),1.77–1.67(m,1H),1.64–1.55(m,1H),1.55–1.46(m,2H),1.29(s,18H),1.17(s,18H),1.03(t,J=7.2 Hz,3H),0.82(s,6H),0.66(s,6H).

[0186] 13 C NMR(126 MHz,CDCl3):δ150.12,150.03,150.00,149.90,146.99,146.93,143.79,143.75,137.93,134.39,134.38,134.31,134.22,134.19,133.71,133.38,132.89,132.85,129.29,128.95,128.85,128.54,128.48,128.08,127.92,127.64,127.36,127.11,127.05,126.78,126.72,126.35,126.14,126.06,126.01,125.82,125.72,125.24,125.03,82.14,32.38,31.48,31.34,30.63,24.40,24.30,23.27,14.24.(Due to C-P couplingand the complexity of the spectrum,doublets in the aromatic region cannot beassigned and they are listed as singlets).

[0187] 31 P NMR(202 MHz,CDCl3):δ28.83.

[0188] 11 B NMR(128 MHz,CDCl3):δ28.48. 10

[0190] 1 H NMR(500 MHz,CDCl3):δ7.86(d,J=8.5 Hz,1H),7.83–7.75(m,6H),7.55–7.50(m,2H),7.48–7.44(m,1H),7.43–7.35(m,6H),7.34–7.27(m,5H),7.24(d,J=4.6 Hz,1H),7.22–7.20(m,2H),7.18–7.14(m,1H),7.12–7.09(m,2H),5.84(d,J=16.0 Hz,1H),3.09–3.00(m,1H),2.96–2.87(m,1H),2.80–2.72(m,1H),2.72–2.63(m,1H),0.89(s,6H),0.62(s,6H).

[0191] 13 C NMR(126 MHz,CDCl3):δ146.48,146.42,145.79,145.75,142.90,137.48,135.20,134.54,134.38,134.25,133.99,133.89,133.71,132.88,132.80,132.32,132.25,131.26,131.10,128.89,128.79,128.29,128.04,127.94,127.85,127.78,127.68,127.52,127.48,127.34,127.22,126.84,126.48,126.31,126.21,125.72,82.51,36.03,32.97,24.53,24.01.(Due to C-P coupling and the complexity of the spectrum,doubletsin the aromatic region cannot be assigned and they are listed as singlets).

[0192] 31P NMR(202 MHz,CDCl3):δ29.26.

[0193] 11 B NMR(160 MHz,CDCl3):δ27.67. 11

[0195] 1 H NMR(500 MHz,CDCl3):δ7.89(d,J=8.5 Hz,1H),7.80(d,J=8.0 Hz,1H),7.76(dd,J=2.2,8.6 Hz,1H),7.75–7.67(m,4H),7.53–7.44(m,2H),7.44–7.34(m,5H),7.30(td,J=1.3,7.4,7.4 Hz,1H),7.23(td,J=2.8,7.2,7.4 Hz,2H),7.17(dd,J=6.4,7.9Hz,2H),7.15–7.10(m,1H),7.08–7.04(m,2H),5.71(d,J=16.0Hz,1H),3.91–3.83(m,1H),3.80–3.70(m,1H),2.71–2.64(m,1H),2.59–2.53(m,1H),2.23–2.13(m,1H),2.13–2.06(m,1H),0.86(s,6H),0.58(s,6H).

[0196] 13C NMR(126 MHz,CDCl3):δ146.75,146.71,146.70,146.63,137.41,135.53,134.70,134.67,134.58,134.56,134.07,134.00,133.97,133.19,132.75,132.68,132.28,132.21,131.35,131.33,131.15,131.13,128.87,128.77,128.29,128.08,127.98,127.96,127.87,127.62,127.60,127.58,127.11,126.94,126.66,126.25,126.15,82.61,45.93,33.01,27.83,24.57,23.91.(Due to C-P coupling and the complexity of thespectrum,doublets in the aromatic region cannot be assigned and they arelisted as singlets).

[0197] 31 P NMR(202 MHz,CDCl3):δ29.08.

[0198] 11 B NMR(128 MHz,CDCl3):δ30.82. 12

[0200] 1 H NMR(500 MHz,CDCl3):δ7.91(d,J=8.5 Hz,1H),7.80(d,J=8.1 Hz,1H),7.78–7.72(m,3H),7.71(d,J=7.0 Hz,1H),7.54–7.47(m,2H),7.46–7.41(m,1H),7.41–7.37(m,1H),7.37–7.30(m,3H),7.32–7.22(m,2H),7.20(t,J=7.3Hz,2H),7.17–7.12(m,2H),7.12–7.07(m,2H),5.81(d,J=16.0 Hz,1H),2.36–2.21(m,2H),1.75–1.59(m,1H),1.59–1.45(m,1H),1.45–1.37(m,4H),0.94(t,J=7.2,3H),0.85(s,6H),0.61(s,6H).

[0201] 13 C NMR(126 MHz,CDCl3):δ146.47,146.40,144.86,144.82,137.68,135.23,134.85,134.63,134.40,134.12,134.03,133.75,132.99,132.91,132.43,132.36,131.21,131.19,131.11,131.09,129.05,128.95,128.37,128.34,128.30,127.93,127.84,127.72,127.62,127.54,127.46,127.39,126.86,126.51,126.34,126.24,82.50,32.47,30.99,29.82,24.51,24.05,22.63,14.29.(Due to C-P coupling and the complexity of thespectrum,doublets in the aromatic region cannot be assigned and they arelisted as singlets).

[0202] 31 P NMR(202 MHz,CDCl3):δ28.94.

[0203] 11 B NMR(128 MHz,CDCl3):δ32.19. 13

[0205] 1H NMR(500 MHz,CDCl3):δ7.93–7.88(m,1H),7.78(d,J=8.0 Hz,1H),7.77–7.68(m,5H),7.50–7.44(m,2H),7.46–7.39(m,1H),7.41–7.37(m,1H),7.36–7.29(m,3H),7.28–7.22(m,3H),7.17(t,J=7.3,7.3 Hz,2H),7.14–7.10(m,1H),7.10–7.07(m,2H),5.80(d,J=16.0 Hz,1H),3.51(t,J=6.9,6.9 Hz,2H),2.50–2.41(m,1H),2.41–2.32(m,1H),2.02(p,J=7.0,7.0,7.1,7.1 Hz,2H),1.85–1.69(m,2H),0.85(s,6H),0.59(s,6H).

[0206] 13 C NMR(126 MHz,CDCl3):δ146.53,146.46,145.91,145.87,137.41,135.25,134.50,134.43,134.20,134.00,133.90,133.69,132.76,132.68,132.22,132.15,131.19,131.17,131.06,131.04,128.84,128.74,128.24,128.02,127.94,127.85,127.78,127.69,127.50,127.09,126.83,126.53,126.21,126.11,82.49,34.20,33.06,29.69,28.49,24.48,23.90.(Due to C-P coupling and the complexity ofthe spectrum,doubletsin the aromatic region cannot be assigned and they are listed as singlets). 31 PNMR(202 MHz,CDCl3):δ28.92.

[0207] 11 B NMR(128 MHz,CDCl3):δ31.47. 14

[0209] 1H NMR(500 MHz,CDCl3):δ7.91(d,J=8.5 Hz,1H),7.85–7.68(m,6H),7.57–7.46(m,2H),7.46–7.35(m,3H),7.35–7.27(m,5H),7.13(t,J=7.4 Hz,1H),7.07(td,J=1.2,7.4 Hz,1H),7.02(d,J=15.9 Hz,1H),6.98(d,J=7.4 Hz,1H),6.06(d,J=16.0 Hz,1H),2.28–2.16(m,2H),1.85(s,3H),1.68–1.55(m,1H),1.55–1.47(m,1H),1.46–1.38(m,2H),0.98(t,J=7.2 Hz,3H),0.86(s,6H),0.62(s,6H).

[0210] 13 C NMR(126 MHz,CDCl3):δ146.47,146.41,145.26,145.22,136.67,136.26,135.16,135.01,134.56,134.55,134.34,134.19,133.99,133.89,133.05,132.98,132.40,132.33,131.86,131.20,131.18,131.12,131.09,130.24,129.59,129.06,128.97,128.45,127.91,127.82,127.67,127.62,127.57,127.53,127.50,127.38,126.45,126.35,126.25,125.86,125.50,82.50,32.40,30.72,24.51,24.03,23.32,19.58,14.24.(Due to C-Pcoupling and the complexity of the spectrum,doublets in the aromatic regioncannot be assigned and they are listed as singlets).

[0211] 31 P NMR(202 MHz,CDCl3):δ28.85.

[0212] 11 B NMR(128 MHz,CDCl3):δ30.30. 15

[0214] 1 H NMR(500 MHz,CDCl3):δ7.91(d,J=8.6 Hz,1H),7.79(d,J=8.1 Hz,1H),7.78–7.69(m,5H),7.54–7.47(m,2H),7.46–7.42(m,1H),7.41–7.31(m,4H),7.28(td,J=2.8,7.6Hz,2H),7.14(d,J=16.0 Hz,1H),7.10(t,J=7.6 Hz,1H),6.96(d,J=7.6 Hz,1H),6.93(d,J=7.8 Hz,1H),6.86(s,1H),5.78(d,J=16.0 Hz,1H),2.34–2.22(m,5H),1.70–1.57(m,1H),1.57–1.48(m,1H),1.47–1.40(m,2H),0.99(t,J=7.2 Hz,3H),0.85(s,6H),0.61(s,6H).

[0215] 13 C NMR(126 MHz,CDCl3):δ146.53,146.46,144.95,144.92,137.78,137.56,135.22,134.76,134.63,134.61,134.39,134.11,134.01,133.95,132.98,132.90,132.44,132.36,131.21,131.19,131.09,131.07,129.02,128.92,128.29,128.22,128.20,128.17,127.94,127.84,127.72,127.62,127.55,127.52,127.38,127.34,126.53,126.32,126.22,82.49,32.40,30.72,24.49,24.02,23.30,21.39,14.23.(Due to C-P coupling and thecomplexity ofthe spectrum,doublets in the aromatic region cannot be assignedand they are listed as singlets).

[0216] 31P NMR(202 MHz,CDCl3):δ29.13.

[0217] 11 B NMR(128 MHz,CDCl3):δ29.59. 16

[0219] 1 H NMR(500 MHz,CDCl3):δ7.90(d,J=8.6 Hz,1H),7.81–7.67(m,6H),7.58–7.46(m,2H),7.45–7.41(m,1H),7.41–7.34(m,2H),7.34–7.26(m,4H),7.06(d,J=16.0 Hz,1H),7.03–6.96(m,4H),5.79(d,J=16.0 Hz,1H),2.29(s,3H),2.27–2.19(m,2H),1.68–1.56(m,1H),1.56–1.46(m,1H),1.46–1.38(m,2H),0.98(t,J=7.2 Hz,3H),0.84(s,6H),0.61(s,6H).

[0220] 13 C NMR(126 MHz,CDCl3):δ146.51,146.44,145.08,145.04,137.37,135.20,134.92,134.63,134.62,134.37,134.14,134.09,134.04,133.81,133.03,132.95,132.48,132.40,131.20,131.18,131.12,131.10,129.11,129.07,128.97,128.29,127.92,127.82,127.70,127.60,127.58,127.52,127.46,126.81,126.50,126.33,126.23,82.48,32.42,30.72,24.51,24.05,23.32,21.35,14.25.(Due to C-P coupling and the complexityof the spectrum,doublets in the aromatic region cannot be assigned and theyare listed as singlets).

[0221] 31P NMR(202 MHz,CDCl3):δ29.11.

[0222] 11 B NMR(128 MHz,CDCl3):δ31.89. 17

[0224] 1 H NMR(500 MHz,CDCl3):δ7.91(d,J=8.5 Hz,1H),7.80(d,J=8.0 Hz,1H),7.80–7.66(m,5H),7.51–7.45(m,2H),7.45–7.39(m,2H),7.37–7.31(m,3H),7.29–7.25(m,2H),7.19–7.12(m,3H),6.99(d,J=8.5 Hz,2H),5.73(d,J=16.0Hz,1H),2.43–2.25(m,2H),1.71–1.61(m,1H),1.56–1.40(m,3H),0.99(t,J=7.2 Hz,3H),0.84(s,6H),0.59(s,6H).

[0225] 13 C NMR(126 MHz,CDCl3):δ146.37,146.31,144.53,144.49,136.23,135.23,134.67,134.65,134.41,134.06,133.97,133.86,132.92,132.84,132.31,132.25,131.26,131.24,131.16,131.14,129.00,128.90,128.86,128.47,128.18,128.01,127.97,127.91,127.75,127.65,127.62,127.59,127.36,127.21,126.61,126.36,126.26,82.54,32.37,30.78,24.48,24.00,23.30,14.23.(Due to C-P coupling and the complexity of thespectrum,doublets in the aromatic region cannot be assigned and they arelisted as singlets).

[0226] 31P NMR(202 MHz,CDCl3):δ28.87.

[0227] 11 B NMR(128 MHz,CDCl3):δ29.78. 18

[0229] 1 H NMR(500 MHz,CDCl3):δ8.09(d,J=8.5 Hz,1H),7.98(d,J=8.1 Hz,1H),7.98–7.84(m,5H),7.71–7.63(m,2H),7.60(dd,J=8.1,15.5 Hz,2H),7.55–7.48(m,3H),7.48–7.41(m,2H),7.37(d,J=16.0 Hz,1H),7.26(d,J=8.7 Hz,2H),7.21(d,J=8.4 Hz,2H),5.93(d,J=16.0 Hz,1H),2.61–2.42(m,2H),1.89–1.79(m,1H),1.75–1.57(m,3H),1.17(t,J=7.2 Hz,3H),1.02(s,6H),0.77(s,6H).

[0230] 13 C NMR(126 MHz,CDCl3):δ148.34,146.41,146.34,144.46,144.42,136.49,135.23,134.67,134.66,134.57,134.40,134.07,133.98,133.75,132.90,132.82,132.29,132.21,131.98,131.29,131.28,131.16,131.15,129.18,129.00,128.90,128.11,128.03,127.95,127.78,127.68,127.66,127.61,127.29,127.17,126.65,126.37,126.27,120.85,82.56,32.38,30.81,24.48,23.99,23.31,14.23.(Due to C-P coupling and thecomplexity of the spectrum,doublets in the aromatic region cannot be assignedand they are listed as singlets).

[0231] 31 P NMR(202 MHz,CDCl3):δ28.94.

[0232] 11 B NMR(128 MHz,CDCl3):δ31.29. 19

[0234] 1 H NMR(500 MHz,CDCl3):δ8.01–7.92(m,2H),7.90–7.80(m,2H),7.70(d,J=16.0Hz,1H),7.53–7.50(m,1H),7.46–7.42(m,1H),7.33–7.24(m,2H),7.23(t,J=7.6 Hz,2H),7.20–7.11(m,1H),5.89(d,J=16.0 Hz,1H),5.66–5.49(m,1H),4.99–4.87(m,2H),4.83–4.62(m,2H),2.71(t,J=7.7 Hz,2H),1.67–1.57(m,2H),1.56–1.47(m,2H),1.03(t,J=7.3Hz,3H),0.73(s,6H),0.70(s,6H).

[0235] 13 C NMR(126 MHz,CDCl3):δ166.82,145.25,142.70,137.71,135.04,133.47,133.21,128.56,128.30,127.67,127.54,127.41,127.27,126.97,126.72,126.62,125.75,82.67,77.84,77.56,68.33,32.52,30.43,24.28,24.16,23.03,14.29.

[0236] 11 B NMR(128 MHz,CDCl3):δ30.71. 20

[0238] 1H NMR(500 MHz,CDCl3):δ7.99(d,J=8.6 Hz,1H),7.91(d,J=8.6 Hz,1H),7.87(d,J=8.7 Hz,1H),7.85(d,J=8.4 Hz,1H),7.73(d,J=15.9 Hz,1H),7.52(t,J=7.3 Hz,1H),7.44(t,J=7.6 Hz,1H),7.29(d,J=7.5 Hz,2H),7.23(t,J=7.6 Hz,2H),7.16(t,J=7.2 Hz,1H),5.91(d,J=15.9 Hz,1H),5.62–5.46(m,1H),4.97–4.89(m,2H),4.75–4.66(m,2H),3.81–3.65(m,2H),2.95–2.75(m,2H),2.18–2.03(m,2H),0.73(s,6H),0.68(s,6H).

[0239] 13 C NMR(126 MHz,CDCl3):δ166.52,147.17,142.62,137.48,135.09,134.06,133.35,128.12,127.90,127.64,127.41,127.20,126.90,126.72,126.70,125.73,77.87,77.59,68.43,45.17,33.12,27.61,24.28,24.23.

[0240] 11 B NMR(128 MHz,CDCl3):δ31.02. 21

[0242] 1H NMR(500 MHz,CDCl3):δ7.96(dd,J=5.2,8.6 Hz,2H),7.87–7.80(m,2H),7.64(d,J=16.0 Hz,1H),7.51(t,J=7.1 Hz,1H),7.43(t,J=7.2 Hz,1H),7.17(d,J=8.1 Hz,2H),7.04(d,J=8.1 Hz,2H),5.86(d,J=16.0 Hz,1H),5.62–5.42(m,1H),4.91(dt,J=7.0,10.0 Hz,2H),4.76–4.68(m,2H),2.69(t,J=7.7 Hz,2H),2.28(s,3H),1.66–1.56(m,2H),1.56–1.46(m,2H),1.02(t,J=7.2 Hz,3H),0.72(s,6H),0.69(s,6H).

[0243] 13 C NMR(126 MHz,CDCl3):δ166.90,145.49,142.83,137.60,135.04,134.94,133.51,133.24,129.29,128.37,127.52,127.51,127.39,127.21,126.65,126.58,126.13,125.75,77.83,77.59,68.30,32.55,30.41,24.28,24.16,23.04,21.30,14.30. 11 B NMR(128MHz,CDCl3):δ30.41. 22

[0245] 1 H NMR(500 MHz,CDCl3):δ7.96(d,J=8.6 Hz,1H),7.92(d,J=8.5 Hz,1H),7.88–7.82(m,2H),7.65(d,J=16.0 Hz,1H),7.55–7.49(m,1H),7.47–7.40(m,1H),7.19(s,4H),5.82(d,J=15.9 Hz,1H),5.58–5.50(m,1H),4.95–4.87(m,2H),4.78–4.66(m,2H),2.75–2.60(m,2H),1.64–1.56(m,2H),1.54–1.45(m,2H),1.02(t,J=7.2 Hz,3H),0.72(s,6H),0.69(s,6H).

[0246] 13 C NMR(126 MHz,CDCl3):δ166.71,144.84,142.47,136.22,135.05,133.38,133.18,131.76,128.70,128.18,127.88,127.60,127.46,127.36,126.71,125.72,82.74,77.86,77.50,68.40,32.48,30.46,24.29,24.15,23.01,14.28.

[0247] 11 B NMR(128 MHz,CDCl3):δ30.47. 23

[0249] 1 H NMR(500 MHz,CDCl3):δ7.97(d,J=8.5 Hz,1H),7.95(d,J=8.6 Hz,1H),7.84(t,J=8.1 Hz,2H),7.55–7.47(m,3H),7.44(t,J=7.2 Hz,1H),7.15(t,J=7.5Hz,1H),7.08(t,J=7.0,7.0 Hz,1H),6.99(d,J=7.4 Hz,1H),6.11(d,J=15.8 Hz,1H),5.61–5.50(m,1H),4.93(q,J=6.9 Hz,2H),4.77–4.70(m,2H),2.68(t,J=7.7 Hz,2H),1.82(s,3H),1.62–1.55(m,2H),1.54–1.45(m,2H),1.01(t,J=7.3Hz,3H),0.73(s,6H),0.70(s,6H).

[0250] 13 C NMR(126 MHz,CDCl3):δ167.02,145.57,142.77,136.97,135.92,134.99,133.39,131.79,130.28,128.39,128.34,127.57,127.50,127.42,127.27,126.54,126.16,125.71,125.50,82.70,77.87,77.61,68.36,32.54,30.45,24.33,24.18,23.06,19.46,14.30.

[0251] 11B NMR(128 MHz,CDCl3):δ31.18. 24

[0253] 1 H NMR(500 MHz,CDCl3):δ7.95(t,J=9.0 Hz,2H),7.88–7.80(m,2H),7.67(d,J=16.0 Hz,1H),7.51(t,J=7.3 Hz,1H),7.45–7.41(m,1H),7.17–7.08(m,2H),7.06(s,1H),6.97(d,J=6.8 Hz,1H),5.86(d,J=16.0 Hz,1H),5.60–5.49(m,1H),4.96–4.86(m,2H),4.77–4.62(m,2H),2.70(t,J=7.5 Hz,2H),2.26(s,3H),1.65–1.57(m,2H),1.56–1.47(m,2H),1.03(t,J=7.2 Hz,3H),0.72(s,6H),0.69(s,6H). 13 C NMR(126 MHz,CDCl3):δ166.86,145.34,142.77,138.10,137.63,135.05,133.48,133.41,128.50,128.47,128.34,127.63,127.54,127.53,127.40,127.25,126.79,126.62,125.76,123.72,82.66,77.85,77.60,68.32,32.54,30.42,24.29,24.16,23.03,21.40,14.30.

[0254] 11 B NMR(128 MHz,CDCl3):δ30.83. 25

[0256] 1H NMR(500 MHz,CDCl3):δ7.97(t,J=9.0 Hz,2H),7.90–7.82(m,2H),7.74(d,J=16.0 Hz,1H),7.57–7.54(m,2H),7.54–7.51(m,1H),7.48(d,J=8.3 Hz,2H),7.45(t,J=7.1 Hz,1H),7.41(t,J=7.7 Hz,2H),7.35(d,J=8.3 Hz,2H),7.31(t,J=7.4 Hz,1H),5.92(d,J=16.0 Hz,1H),5.61–5.46(m,1H),5.03–4.87(m,2H),4.83–4.60(m,2H),2.72(t,J=7.7 Hz,2H),1.66–1.59(m,2H),1.57–1.48(m,2H),1.04(t,J=7.2 Hz,3H),0.73(s,6H),0.70(s,6H).

[0257] 13 C NMR(126 MHz,CDCl3):δ166.85,145.30,142.70,140.78,140.38,136.80,135.08,133.49,132.74,128.88,128.32,127.58,127.45,127.39,127.32,127.26,127.18,127.06,126.98,126.68,125.79,77.88,77.61,68.37,32.57,30.49,24.31,24.18,23.07,14.32.

[0258] 11 B NMR(128 MHz,CDCl3):δ30.15. 26

[0260] 1H NMR(500 MHz,CDCl3):δ7.95(dd,J=6.3,8.2 Hz,2H),7.88–7.79(m,2H),7.60(d,J=16.0 Hz,1H),7.50(t,J=7.4 Hz,1H),7.43(t,J=7.6 Hz,1H),7.34–7.24(m,2H),7.23(d,J=8.1 Hz,2H),7.06(t,J=7.4 Hz,1H),6.95(d,J=7.7 Hz,2H),6.87(d,J=8.7Hz,2H),5.85(d,J=16.0 Hz,1H),5.60–5.42(m,1H),5.04–4.86(m,2H),4.76–4.67(m,2H),2.68(t,J=6.9 Hz,2H),1.66–1.56(m,2H),1.55–1.44(m,2H),1.01(t,J=7.3 Hz,3H),0.72(s,6H),0.68(s,6H).

[0261] 13 C NMR(126 MHz,CDCl3):δ166.81,157.20,156.88,145.31,142.74,135.03,133.46,132.99,132.41,129.82,128.29,128.10,127.55,127.53,127.41,127.25,126.63,126.21,125.73,123.38,118.98,118.92,82.64,77.89,77.54,68.34,32.53,30.40,24.28,24.16,23.02,14.30.

[0262] 11 B NMR(128 MHz,CDCl3):δ31.05. 27

[0264] 1H NMR(500 MHz,CDCl3):δ7.99(dd,J=3.5,8.1 Hz,2H),7.89(d,J=8.5 Hz,1H),7.86(d,J=8.0 Hz,1H),7.82(d,J=15.9 Hz,1H),7.77–7.71(m,2H),7.66–7.60(m,2H),7.56–7.50(m,1H),7.49(s,1H),7.47–7.43(m,1H),7.39–7.36(m,2H),6.06(d,J=15.9 Hz,1H),5.60–5.52(m,1H),4.96–4.86(m,2H),4.78–4.69(m,2H),2.75(t,J=7.7 Hz,2H),1.69–1.59(m,2H),1.59–1.48(m,2H),1.05(t,J=7.3 Hz,3H),0.74(s,6H),0.71(s,6H).

[0265] 13 C NMR(126 MHz,CDCl3):δ166.86,145.31,142.73,135.21,135.10,133.67,133.52,133.33,133.10,128.33,128.20,128.01,127.71,127.60,127.59,127.49,127.33,127.32,127.14,126.70,126.30,125.93,125.79,123.54,82.71,77.85,77.58,68.39,32.56,30.52,24.32,24.19,23.08,14.33.

[0266] 11 B NMR(128 MHz,CDCl3):δ30.60. 28

[0268] 1H NMR(500 MHz,CDCl3):δ8.00(d,J=8.7 Hz,1H),7.92(d,J=8.3 Hz,1H),7.80(dd,J=6.2,8.4 Hz,2H),7.55(d,J=16.0 Hz,1H),7.48–7.44(m,1H),7.40–7.36(m,1H),7.23–7.18(m,6H),7.16–7.11(m,1H),7.01(d,J=7.9 Hz,2H),5.86(d,J=15.9 Hz,1H),5.25(d,J=12.3 Hz,1H),5.16(d,J=12.3 Hz,1H),2.64–2.48(m,2H),1.55–1.49(m,2H),1.49–1.42(m,2H),0.98(t,J=7.2 Hz,3H),0.70(s,6H),0.61(s,6H).

[0269] 13 C NMR(126 MHz,CDCl3):δ167.55,145.88,142.40,137.85,137.56,134.97,133.60,133.36,132.90,129.04,128.42,128.40,128.23,128.12,127.47,127.41,127.21,126.97,126.79,126.31,126.18,14.25.

[0270] 11 B NMR(128 MHz,CDCl3):δ32.16. 29

[0272] 1H NMR(500 MHz,CDCl3):δ8.03(d,J=8.6 Hz,1H),7.95(d,J=8.5 Hz,1H),7.84(t,J=8.1 Hz,2H),7.60(d,J=16.0 Hz,1H),7.52–7.47(m,1H),7.45–7.39(m,1H),7.24(d,J=4.4 Hz,4H),7.20–7.12(m,1H),6.87(d,J=1.4 Hz,1H),6.83(dd,J=1.5,7.9 Hz,1H),6.67(d,J=7.9 Hz,1H),5.91–5.87(m,3H),5.22(d,J=12.2 Hz,1H),5.14(d,J=12.2Hz,1H),2.70–2.51(m,2H),1.60–1.54(m,2H),1.53–1.47(m,2H),1.03(t,J=7.2 Hz,3H),0.73(s,6H),0.64(s,6H).

[0273] 13 C NMR(126 MHz,CDCl3):δ167.52,147.66,147.35,145.76,142.37,137.79,134.98,133.57,132.93,130.17,128.44,128.21,128.04,127.48,127.27,127.24,127.00,126.74,126.35,126.11,122.15,109.19,108.05,101.06,82.47,66.46,32.61,30.34,24.13,23.05,14.25.

[0274] 11 B NMR(128 MHz,CDCl3):δ29.30. 30

[0276] 1H NMR(500 MHz,CDCl3):δ7.98(d,J=8.7 Hz,1H),7.92(d,J=8.3 Hz,1H),7.84–7.77(m,2H),7.61(d,J=16.0 Hz,1H),7.50–7.45(m,1H),7.44(dd,J=0.8,1.5 Hz,1H),7.42–7.36(m,1H),7.27(t,J=1.7 Hz,1H),7.24–7.19(m,4H),7.16–7.11(m,1H),6.36(d,J=1.1 Hz,1H),5.86(d,J=16.0 Hz,1H),5.16(d,J=12.6Hz,1H),5.08(d,J=12.6 Hz,1H),2.69–2.52(m,2H),1.59–1.53(m,2H),1.53–1.44(m,2H),1.01(t,J=7.2 Hz,3H),0.70(s,6H),0.61(s,6H).

[0277] 13 C NMR(126 MHz,CDCl3):δ167.45,145.82,143.08,142.49,141.45,137.84,134.99,133.59,132.92,128.49,128.25,127.97,127.55,127.49,127.31,127.28,127.03,126.76,126.38,126.05,120.86,110.89,82.51,58.11,32.64,30.36,24.17,24.16,23.06,14.30.

[0278] 11 B NMR(128 MHz,CDCl3):δ31.31. 31

[0280] 1H NMR(500 MHz,CDCl3):δ8.00(d,J=8.6 Hz,1H),7.93(d,J=8.5 Hz,1H),7.81(t,J=8.8 Hz,2H),7.59(d,J=16.0 Hz,1H),7.50–7.44(m,1H),7.43–7.35(m,1H),7.26–7.17(m,5H),7.17–7.10(m,2H),7.02(dd,J=1.1,5.0 Hz,1H),5.87(d,J=16.0 Hz,1H),5.29(d,J=12.6 Hz,1H),5.22(d,J=12.6 Hz,1H),2.74–2.48(m,2H),1.59–1.50(m,2H),1.50–1.42(m,2H),0.99(t,J=7.2 Hz,3H),0.70(s,6H),0.61(s,6H).

[0281] 13 C NMR(126 MHz,CDCl3):δ167.43,145.81,142.48,137.81,137.27,135.00,133.59,132.91,128.49,128.25,127.99,127.77,127.56,127.49,127.37,127.28,127.03,126.79,126.38,126.12,125.76,123.81,82.51,61.79,32.62,30.35,24.19,24.15,23.05,14.29.

[0282] 11 B NMR(128 MHz,CDCl3):δ31.48. 32

[0284] 1H NMR(500 MHz,CDCl3):δ7.90(d,J=8.4 Hz,1H),7.77(d,J=7.7 Hz,1H),7.73(d,J=8.4 Hz,1H),7.67(d,J=15.9 Hz,1H),7.45–7.33(m,7H),7.27–7.23(m,3H),7.17–7.13(m,5H),7.12–7.08(m,1H),7.03–7.00(m,2H),5.74(d,J=15.9 Hz,1H),2.84(ddd,J=6.2,9.0,13.1 Hz,1H),2.69(ddd,J=6.2,9.1,13.1 Hz,1H),1.77–1.61(m,2H),1.59–1.50(m,2H),1.02(t,J=7.3Hz,3H),0.77(s,6H),0.54(s,6H).

[0285] 13 C NMR(126MHz,CDCl3):δ148.21,147.93,147.16,147.09,140.35,140.24,138.66,138.55,137.66,134.90,134.12,133.95,133.90,133.87,133.66,133.59,133.29,133.14,131.09,128.28,128.25,128.22,128.06,127.88,127.84,127.65,127.63,127.50,127.44,127.30,127.28,126.84,126.76,126.43,126.00,82.50,32.90,30.57,24.43,23.85,23.06,14.36.(Due to C-P coupling and the complexity of the spectrum,doublets in the aromatic region cannot be assigned and they are listed assinglets).

[0286] 31 P NMR(202MHz,CDCl3):δ-15.15.

[0287] 11 B NMR(160MHz,CDCl3):δ28.09. 33

[0289] 1 H NMR (400MHz, CDCl3): δ7.33–7.15(m,10H),6.48(d,J=15.7Hz,1H),6.33(dd,J=15.7,8.5 Hz,1H),4.27(dd,J=10.9,8.5Hz,1H),3.96(d,J=10.9Hz,1H),3.69(s,3H),3.51(s,3H).

[0290] 13 C NMR (101MHz, CDCl3): δ168.31,167.89,140.27,136.92,131.94,129.21,12 8.83,128.58,127.97,127.68,127.28,126.49,57.75,52.73,52.55,49.30.

[0291] The above description is only a preferred embodiment of the present invention. All equivalent changes and modifications made within the scope of the claims of the present invention should be included in the scope of the present invention.

Claims

1. A method for preparing a phosphine-containing axially chiral alkenyl borate ester, characterized in that, Includes the following steps: (1) Add aryl-containing 1,3-enyne, phosphine-containing aryl bromide, copper salt, palladium, and ligand to a pressure-resistant sealed reaction vessel. Add diboron reagent and base in a glove box, remove air, fill with argon, add organic solvent, and stir the reaction at 15-40℃ for 72-96 h. (2) Remove the material obtained in step (1) from the pressure-resistant sealed reaction vessel, cool it to room temperature, add ethyl acetate, elute it through a short silica gel column to obtain the crude product, and then use 60... o C was extracted with water three times to extract the organic phase; (3) The organic solvent in the organic phase obtained in step (2) is evaporated, purified by silica gel column chromatography, and then eluted with eluent to obtain the phosphine-containing axial chiral alkenyl borate ester. The aryl-containing 1,3-enyne is an alkyl-substituted aryl-containing 1,3-enyne, an aryl-containing 1,3-enyne without benzene ring substitution, or an aryl-containing 1,3-enyne with benzene ring substitution. The phosphine-containing aryl bromide is a phosphorus-containing aryl bromide with an unsubstituted benzene ring on the phosphine, a phosphorus-containing aryl bromide with a monosubstituted benzene ring on the phosphine, or a phosphorus-containing aryl bromide with a polysubstituted benzene ring on the phosphine. The copper salt is one of 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ethylene copper salt and 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ethylene copper salt; The palladium catalyst is one of palladium acetate and palladium bromide; The ligand is one of (R)-4-(anthra-9-yl)-3-(tert-butyl)-2,3-dihydrobenzo[d][1,3]oxophosphacyclopentadiene, (S)-3-(tert-butyl)-4-(2,6-dimethoxy-3,5-dimethylphenyl)-2,3-dihydrobenzo[d][1,3]oxophosphacyclopentadiene, and (3aS,8aR)-2-(m-methyl)-3a,8a-dihydro-8H-indene[1,2-d]dioxazole; The diboron reagent is pinacol diboronate.

2. The method according to claim 1, characterized in that, The alkali is one of sodium tert-amyl alcohol and sodium tert-butoxide; the organic solvent is one of mesitylene and trifluorotoluene.

3. The method according to claim 1, characterized in that, The eluent is a mixed solution of petroleum ether and ethyl acetate; the volume ratio of petroleum ether to ethyl acetate in the eluent is 10:1-3:1.

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