Preparation method of nickel-catalyzed benzylsilane compound containing ortho-boronic acid pinacol ester

Abstract

The invention discloses a preparation method of a nickel-catalyzed benzylsilane compound containing ortho-boric acid pinacol ester, which comprises the following steps: taking a benzylsilane compound and bis (pinacol ester) borate as raw materials, and reacting in an organic nickel catalyst, phosphine ligand and base catalysis system to obtain the benzylsilane compound containing ortho-boric acid ester. According to the method, the organic nickel catalyst is utilized to realize ortho-position C-H bond activation of the benzyl aromatic hydrocarbon compound and B-B bond breakage of bis (pinacolato) diboron, reduction elimination is carried out at the center of the organic nickel catalyst to selectively generate the benzylsilane compound of ortho-position boric acid ester, the reaction condition is mild, the use of noble metal is avoided, and the reaction cost is reduced.

Description

Technical Field

[0001] This invention relates to a method for preparing a compound, and more particularly to a nickel-catalyzed method for preparing benzylsilane compounds containing pinacol ester of ortho-boronate. Background Technology

[0002] The organoboronal pinacol ester structure is an important structural unit widely used in natural product synthesis, drug design, and functional materials research. Furthermore, the borate pinacol ester structure is also a highly practical building block in organic synthesis, frequently used as an intermediate in the synthesis of drugs and bioactive molecules. The silicon group, too, can serve as a synthon, involved in a series of chemical transformations, and is also an important bioactive group in medicinal chemistry. Therefore, constructing benzylsilane compounds containing ortho-boronal pinacol esters is of significant importance.

[0003] The direct CH-bondation of benzylsilanes under transition metal catalysis is an atomically economical, green, and efficient synthetic strategy for constructing benzylsilanes containing pinacol esters of ortho-boronate. Previously, CH-bondation reactions have been achieved using noble metals (rare metals) such as iridium, rhodium, and ruthenium. However, due to the low abundance and high cost of noble metals, alternative catalysts are needed. Summary of the Invention

[0004] Purpose of the invention: The present invention aims to provide a nickel-catalyzed method for preparing benzylsilane compounds containing ortho-boronic acid pinacol esters. By using nickel as a catalyst to replace the precious metals in the prior art, the cost is reduced, and the method enables the introduction of borate pinacol esters at the ortho position of benzylsilane compounds to generate benzylsilane compounds containing ortho-boronic acid pinacol esters.

[0005] Technical solution: The present invention describes a nickel-catalyzed method for preparing benzylsilane compounds containing ortho-boronic acid pinacol esters. Using benzylsilane compounds and pinacol diboronic acid pinacol esters as raw materials, the method involves reacting them in an organonitrile catalyst, with a phosphine ligand and a base catalytic system to obtain benzylsilane compounds containing ortho-boronic acid esters. The synthetic route is as follows:

[0006]

[0007] B2pin2 is a quinolone ester.

[0008] Preferably, the R 1 Selected from H, C1-C3 alkyl groups; R 3 Selected from H or halogen; R 3 It is selected from H, C1-C3 alkyl, halogen-substituted C1-C3 alkyl, C1-C3 alkoxy, pinacol borate, naphthyl, pyrene, or fused aromatic ring substituted.

[0009] Preferably, the reaction temperature is 50–100°C and the reaction time is 12–24 hours.

[0010] Preferably, the molar ratio of the benzylsilane compound to pinacol diboronate is 1:2 to 4.

[0011] Preferably, the molar ratio of the alkali, phosphine ligand, and organonitrile catalyst is 1:2-4:0.1-0.2:0.05-0.10:0.05-0.10.

[0012] Preferably, the molar ratio of the benzylsilane compound, pinacol diboronate, base, phosphine ligand, and organonitrile catalyst is 1:2-4:0.1-0.2:0.05-0.10:0.05-0.10.

[0013] Preferably, the organonitrile catalyst is bis-(1,5-cyclooctadiene)nickel or nickel trifluoromethanesulfonate.

[0014] Preferably, the phosphine ligand is selected from one or more of tri(methyl)phosphine, tri(ethyl)phosphine, tri(cyclohexyl)phosphine, tri(n-butyl)phosphine, and tri(tert-butyl)phosphine.

[0015] Preferably, the alkali is selected from one or more of sodium tert-butoxide, potassium tert-butoxide, sodium methoxide, potassium methoxide, potassium bis(trimethylsilyl)amino, and sodium bis(trimethylsilyl)amino.

[0016] The reaction is carried out under the protection of an inert gas.

[0017] Preferably, the solvent for the reaction is n-hexane, tetrahydrofuran, or 2-methyltetrahydrofuran.

[0018] Preferably, the benzylsilane compound containing ortho-boronate has the following structural formula:

[0019]

[0020] Mechanism of Invention: In this invention, an organonitrogen catalyst is used to generate a nickel-boron anionic complex [Ni(II)]-(H)(Bpin)(SiR3) complex I with benzylsilane and pinacol ester of borate (B2pin2) under the action of a catalytic amount of base. In complex I, the ortho-CH bond of the benzene ring is drawn closer to the nickel center and activated, and the CH bond breaks through a hydrogen transfer process to form a cyclometalated nickel intermediate II. After the cyclometalated nickel intermediate II dissociates and releases one molecule of HBpin, it yields a cyclometalated nickel intermediate III. Subsequently, intermediate III further complexes with one molecule of B2pin2, undergoing oxidative addition of the BB bond to obtain intermediate IV. In intermediate IV, a reductive elimination of the CB bond occurs to obtain intermediate V. Finally, intermediate V releases benzylsilane containing pinacol ester of ortho-boron silane through ligand exchange with benzylsilane, while regenerating the reactive catalytic species nickel-boron anionic complex I. The catalytic process is described in [details omitted]. Figure 2 .

[0021] Beneficial effects: Compared with the prior art, the present invention has the following significant advantages: (1) It utilizes an organonitrile catalyst to activate the ortho-CH bond of benzyl aromatic compounds and break the BB bond of pinacol ester of borate, thereby achieving selective generation of benzyl silane compounds of ortho-boron ester by reductive elimination at the center of the organonitrile catalyst; (2) The reaction conditions are mild and avoid the use of precious metals, thus reducing the reaction cost. Attached Figure Description

[0022] Figure 1 This is the synthetic route of the present invention;

[0023] Figure 2 This is a diagram illustrating the catalytic mechanism of the present invention. Detailed Implementation

[0024] The technical solution of the present invention will be further described below with reference to the embodiments.

[0025] Example 1

[0026] The method for preparing nickel-catalyzed benzylsilane compounds containing ortho-boronic acid pinacol esters according to the present invention includes the following steps:

[0027] Prepare benzyl dimethylsilane (30.0 mg, 0.2 mmol, 1.0 equiv.), pinacol diboronate (152.4 mg, 0.6 mmol, 3.0 equiv.), and tri(methyl)phosphine (20 μL, 0.02 mmol, 1.0 M in). THF), bis(trimethylsilyl)aminopotassium (8.0 mg, 0.04 mmol), bis-(1,5-cyclooctadiene)nickel (5.5 mg, 0.02 mmol), tetrahydrofuran 0.5 mL, under nitrogen protection, sealed at 80 °C for 12 h, cooled, solvent recovered under reduced pressure, and separated by column chromatography (stationary phase: 200-300 mesh silica gel, mobile phase: petroleum ether: ethyl acetate = 50:1) to obtain 25.4 mg of dimethyl(2-(4,4,5,5-tetramethyl-1,3,2-dioxoboronyl-2-yl)benzyl)silane, yield 46%, with the following structural formula:

[0028]

[0029] Its structure was confirmed by NMR analysis; 1 H NMR(400MHz,Chloroform-d)δ7.77(dd,J=8,2Hz,1H),7.29(td,J=8,2Hz,1H),7.07(td,J=8,1Hz, 1H),7.04–7.01(m,1H),3.93–3.83(m,1H),2.59(d,J=3Hz,2H),1.34(s,12H),0.05(d,J=4Hz,6H). 13 C{H}NMR (101MHz, Chloroform-d): δ147.7,136.4,130.8,128.7,123.4,83.3,24.9,24.3,-4.4.

[0030] Example 2

[0031] The method for preparing nickel-catalyzed benzylsilane compounds containing ortho-boronic acid pinacol esters according to the present invention includes the following steps:

[0032] (1) Preparation of (2-fluorobenzyl)dimethylsilane:

[0033] Under anhydrous and oxygen-free conditions, magnesium powder (1.10 g, 45.8 mmol), THF (7.0 mL), dichloromethylsilane (5.0 mL, 45.0 mmol), and elemental iodine (5–10 grains) were added to a dry 100 mL three-necked round-bottom flask (equipped with a magnetic stir bar, reflux condenser, and constant-pressure dropping funnel). Then, 1-chloromethyl-2-fluorobenzene (1.9 g, 13.0 mmol) was slowly added dropwise to the flask, and the reaction mixture was heated to reflux. After two hours of reaction, the reaction mixture was cooled to room temperature, and TLC analysis confirmed complete consumption of benzyl chloride. After the reaction was complete, the reaction mixture was diluted with 50 mL of petroleum ether, filtered, and washed with petroleum ether to obtain the reaction mixture. The solvent was removed by rotary evaporation, and the purified product (stationary phase: 200–300 mesh silica gel; mobile phase: petroleum ether) was obtained by rapid column chromatography with a yield of 91%. The synthetic route is as follows:

[0034]

[0035] (2) Preparation of benzylsilane compounds containing ortho-boron pinacol ester:

[0036] Take (2-fluorobenzyl)dimethylsilane (33.6 mg, 0.2 mmol, 1.0 equiv.), pinacol diboronate (152.4 mg, 0.6 mmol, 3.0 equiv.), and tri(methyl)phosphine (20 μL, 0.02 mmol, 1.0 M in). THF), bis(trimethylsilyl)aminopotassium (8.0 mg, 0.04 mmol), bis-(1,5-cyclooctadiene)nickel (5.5 mg, 0.02 mmol), tetrahydrofuran 0.5 mL, under nitrogen protection, sealed at 80 °C for 12 h, cooled, solvent recovered under reduced pressure, separated by column chromatography (stationary phase: 200-300 mesh silica gel, mobile phase: petroleum ether: ethyl acetate = 50:1) to obtain 33.5 mg of (2-fluoro-6-(4,4,5,5-tetramethyl-1,3,2-dioxoboronyl-2-yl)benzyl)dimethylsilane, yield 57%, with the following structural formula:

[0037]

[0038] Its structure was confirmed by NMR analysis; 1 H NMR (400MHz, Chloroform-d) δ7.57–7.52(m,1H),7.08–7.02(m,2H),3.94–3.86(m,1H),2.60(t,J=3Hz,2H),1.34(s,12H),0.07(d,J=4Hz,6H). 13C{H}NMR(101MHz,Chloroform-d)δ160.2(d,J=242Hz),134.4(d,J=15Hz),131.8( d, J=3Hz), 124.7 (d, J=8Hz), 117.4 (d, J=23Hz), 83.6, 24.9, 15.9 (d, J=4Hz), -4.2.

[0039] Example 3

[0040] The method for preparing nickel-catalyzed benzylsilane compounds containing ortho-boronic acid pinacol esters according to the present invention includes the following steps:

[0041] (1) Preparation of (3-methoxybenzyl)dimethylsilane:

[0042] Under anhydrous and oxygen-free conditions, magnesium powder (1.10 g, 45.8 mmol), THF (7.0 mL), dichloromethylsilane (5.0 mL, 45.0 mmol), and elemental iodine (5–10 grains) were added to a dry 100 mL three-necked round-bottom flask (equipped with a magnetic stir bar, reflux condenser, and constant-pressure dropping funnel). Then, 1-chloromethyl-3-methoxybenzene (2.0 g, 13.0 mmol) was slowly added dropwise to the flask, and the reaction mixture was heated to reflux. After reacting for two hours, the reaction mixture was cooled to room temperature, and TLC analysis confirmed complete consumption of benzyl chloride. After the reaction was complete, the reaction mixture was diluted with 50 mL of petroleum ether, filtered, and washed with petroleum ether to obtain the reaction mixture. The solvent was removed by rotary evaporation, and the purified product (stationary phase: 200–300 mesh silica gel; mobile phase: petroleum ether) was obtained by rapid column chromatography in 83% yield. The synthetic route is as follows:

[0043]

[0044] (2) Preparation of benzylsilane compounds containing ortho-boron pinacol ester:

[0045] Take (3-methoxybenzyl)dimethylsilane (36.0 mg, 0.2 mmol, 1.0 equiv.), pinacol diboronate (152.4 mg, 0.6 mmol, 3.0 equiv.), and tri(methyl)phosphine (20 μL, 0.02 mmol, 1.0 M in). THF), bis(trimethylsilyl)aminopotassium (8.0 mg, 0.04 mmol), bis-(1,5-cyclooctadiene)nickel (5.5 mg, 0.02 mmol), tetrahydrofuran 0.5 mL, under nitrogen protection, sealed at 80 °C for 12 h, cooled, solvent recovered under reduced pressure, and separated by column chromatography (stationary phase: 200-300 mesh silica gel, mobile phase: petroleum ether: ethyl acetate = 50:1) to obtain 24.5 mg of (5-methoxy-2-(4,4,5,5-tetramethyl-1,3,2-dioxoboronyl-2-yl)benzyl)dimethylsilane, yield 40%, with the following structural formula:

[0046]

[0047] Its structure was confirmed by NMR analysis; 1 H NMR(400MHz,Chloroform-d)δ7.72(d,J=8Hz,1H),6.62(dd,J=8,2Hz,1H),6.56(d,J=2Hz,1 H),3.93–3.83(m,1H),3.79(s,3H),2.57(d,J=3Hz,2H),1.32(s,12H),0.05(d,J=4Hz,6H). 13 C{H}NMR(101MHz,Chloroform-d)δ161.7,150.0,138.2,114.2,109.0,83.0,54.9,24.9,24.5,-4.4.

[0048] Example 4

[0049] The method for preparing nickel-catalyzed benzylsilane compounds containing ortho-boronic acid pinacol esters according to the present invention includes the following steps:

[0050] (1) Preparation of (4-methoxybenzyl)dimethylsilane:

[0051] Under anhydrous and oxygen-free conditions, magnesium powder (1.10 g, 45.8 mmol), THF (7.0 mL), dichloromethylsilane (5.0 mL, 45.0 mmol), and elemental iodine (5–10 grains) were added to a dry 100 mL three-necked round-bottom flask (equipped with a magnetic stir bar, reflux condenser, and constant-pressure dropping funnel). Then, 1-chloromethyl-4-methoxybenzene (2.0 g, 13.0 mmol) was slowly added dropwise to the flask, and the reaction mixture was heated to reflux. After reacting for two hours, the reaction mixture was cooled to room temperature, and TLC analysis confirmed complete consumption of benzyl chloride. After the reaction was complete, the reaction mixture was diluted with 50 mL of petroleum ether, filtered, and washed with petroleum ether to obtain the reaction mixture. The solvent was removed by rotary evaporation, and the purified product (stationary phase: 200–300 mesh silica gel; mobile phase: petroleum ether) was obtained by rapid column chromatography in 93% yield. The synthetic route is as follows:

[0052]

[0053] (2) Preparation of benzylsilane compounds containing ortho-boron pinacol ester:

[0054] Prepare (4-methoxybenzyl)dimethylsilane (36 mg, 0.2 mmol, 1.0 equiv.), pinacol diboronate (152.4 mg, 0.6 mmol, 3.0 equiv.), and tri(methyl)phosphine (20 μL, 0.02 mmol, 1.0 M in). THF), bis(trimethylsilyl)aminopotassium (8.0 mg, 0.04 mmol), bis-(1,5-cyclooctadiene)nickel (5.5 mg, 0.02 mmol), tetrahydrofuran 0.5 mL, under nitrogen protection, sealed at 80 °C for 12 h, cooled, solvent recovered under reduced pressure, and separated by column chromatography (stationary phase: 200-300 mesh silica gel, mobile phase: petroleum ether: ethyl acetate = 50:1) to obtain 26.8 mg of (4-methoxy-2-(4,4,5,5-tetramethyl-1,3,2-dioxoboronyl-2-yl)benzyl)dimethylsilane, yield 31%, with the following structural formula:

[0055]

[0056] Its structure was confirmed by NMR analysis; 1 H NMR(400MHz,Chloroform-d)δ7.31(d,J=3Hz,1H),6.95(d,J=8Hz,1H),6.87(dd,J=8,3Hz,1 H),3.91–3.81(m,1H),3.80(s,3H),2.51(d,J=3Hz,2H),1.34(s,12H),0.04(d,J=4Hz,6H). 13C{H}NMR(101MHz,Chloroform-d)δ155.9,139.6,129.8,120.3,117.4,83.4,55.3,24.9,22.9,-4.4.

[0057] Example 5

[0058] The method for preparing nickel-catalyzed benzylsilane compounds containing ortho-boronic acid pinacol esters according to the present invention includes the following steps:

[0059] (1) Preparation of dimethyl(1-phenylethyl)silane:

[0060] Under anhydrous and oxygen-free conditions, magnesium powder (1.10 g, 45.8 mmol), THF (7.0 mL), dichlorodimethylsilane (5.0 mL, 45.0 mmol), and elemental iodine (5–10 grains) were added to a dry 100 mL three-necked round-bottom flask (equipped with a magnetic stir bar, reflux condenser, and constant-pressure dropping funnel). Then, (1-chloroethyl)benzene (1.8 g, 13.0 mmol) was slowly added dropwise to the flask, and the reaction mixture was heated to reflux. After two hours of reaction, the reaction mixture was cooled to room temperature, and TLC analysis confirmed complete consumption of benzyl chloride. After the reaction was complete, the reaction mixture was diluted with 50 mL of petroleum ether, filtered, and washed with petroleum ether to obtain the reaction mixture. The solvent was removed by rotary evaporation, and the purified product (stationary phase: 200–300 mesh silica gel; mobile phase: petroleum ether) was obtained by rapid column chromatography in 85% yield. The synthetic route is as follows:

[0061]

[0062] (2) Preparation of benzylsilane compounds containing ortho-boron pinacol ester:

[0063] Prepare dimethyl(1-phenylethyl)silane (32.8 mg, 0.2 mmol, 1.0 equiv.), pinacol diboronate (152.4 mg, 0.6 mmol, 3.0 equiv.), and tri(methyl)phosphine (20 μL, 0.02 mmol, 1.0 M in). THF), bis(trimethylsilyl)aminopotassium (8.0 mg, 0.04 mmol), bis-(1,5-cyclooctadiene)nickel (5.5 mg, 0.02 mmol), tetrahydrofuran 0.5 mL, under nitrogen protection, sealed at 80 °C for 12 h, cooled, solvent recovered under reduced pressure, and separated by column chromatography (stationary phase: 200-300 mesh silica gel, mobile phase: petroleum ether: ethyl acetate = 50:1) to obtain 30.2 mg of dimethyl(1-(2-(4,4,5,5-tetramethyl-1,3,2-dioxoboronyl-2-yl)phenyl)ethyl)silane, yield 52%). The structural formula is:

[0064]

[0065] Its structure was confirmed by NMR analysis; 1 H NMR(400MHz,Chloroform-d)δ7.77(dd,J=8,2Hz,1H),7.37(td,J=8,2Hz,1H),7.15(dd,J=8,1Hz,1H),7.09(td,J=8, 1Hz,1H),3.83–3.72(m,1H),3.41–3.29(m,1H),1.40(d,J=8Hz,3H),1.35(s,12H),0.03–-0.02(m,3H),-0.01(s,3H). 13 C{H}NMR(101MHz,Chloroform-d)δ152.9,136.1,130.9,125.3,123.4,83.3,25.1,24.9,15.2,-5.3,-6.4.

[0066] Example 6

[0067] The method for preparing nickel-catalyzed benzylsilane compounds containing ortho-boronic acid pinacol esters according to the present invention includes the following steps:

[0068] (1) Preparation of dimethyl(4-(4,4,5,5-tetramethyl-1,3,2-dioxoborane-2-yl)benzyl)silane:

[0069] Magnesium powder (0.55 g, 22.9 mmol), THF (5.0 mL), dichlorodimethylsilane (2.5 mL, 22.5 mmol), and elemental iodine (5–10 grains) were added to a dry 100 mL three-necked round-bottom flask (equipped with a magnetic stir bar, reflux condenser, and constant-pressure dropping funnel). Then, 2-(4-(chloromethyl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxoborane (1.9 g, 6.5 mmol) was slowly added dropwise to the flask, and the reaction mixture was heated to reflux. After reacting for two hours, the reaction mixture was cooled to room temperature, and TLC analysis confirmed complete consumption of benzyl chloride. After the reaction was complete, the reaction mixture was diluted with 50 mL of petroleum ether, filtered, and washed with petroleum ether to obtain the reaction mixture. The solvent was removed by rotary evaporation, and the purified product (stationary phase: 200–300 mesh silica gel; mobile phase: petroleum ether) was obtained by rapid column chromatography in 87% yield. The synthetic route is as follows:

[0070]

[0071] (2) Preparation of benzylsilane compounds containing ortho-boron pinacol ester:

[0072] Prepare dimethyl (4-(4,4,5,5-tetramethyl-1,3,2-dioxoboronyl-2-yl)benzyl)silane (55 mg, 0.2 mmol, 1.0 equiv.), pinacol diboronate (152.4 mg, 0.6 mmol, 3.0 equiv.), and tri(methyl)phosphine (20 μL, 0.02 mmol, 1.0 M in). THF), bis(trimethylsilyl)aminopotassium (8.0 mg, 0.04 mmol), bis-(1,5-cyclooctadiene)nickel (5.5 mg, 0.02 mmol), tetrahydrofuran 0.5 mL, under nitrogen protection, sealed at 80 °C for 12 h, cooled, solvent recovered under reduced pressure, separated by column chromatography (stationary phase: 200-300 mesh silica gel, mobile phase: petroleum ether: ethyl acetate 20:1) to obtain 29.8 mg of (2,4-bis(4,4,5,5-tetramethyl-1,3,2-dioxoboronyl-2-yl)benzyl)dimethylsilane, yield 37%, structural formula:

[0073]

[0074] Its structure was confirmed by NMR analysis; 1 H NMR(400MHz,Chloroform-d)δ8.21(d,J=2Hz,1H),7.73(dd,J=8,2Hz,1H),7.03(d,J =8Hz,1H),3.90–3.83(m,1H),2.62(d,J=3Hz,2H),1.33(s,24H),0.03(d,J=4Hz,6H). 13 C{H}NMR(101MHz,Chloroform-d)δ151.4,143.0,137.2,128.2,83.5,83.3,24.9,24.9,-4.4.

[0075] Example 7

[0076] The method for preparing nickel-catalyzed benzylsilane compounds containing ortho-boronic acid pinacol esters according to the present invention includes the following steps:

[0077] (1) Preparation of (4-(1-(dimethylsilyl)ethyl)phenyl)trimethylsilane:

[0078] In a glove box, trimethyl(4-vinylphenyl)silane (352 mg, 2.0 mmol) and O(SiMe2H)2 (1.8 mL, 10 mmol) were added to a 10.0 mL reaction tube. Subsequently, ultradry THF (1.0 mL) and KOtBu (0.4 mmol) were added to the reaction mixture. The reaction mixture was heated to 80 °C and reacted for 48 hours, then cooled to room temperature. The reaction mixture was diluted with 10.0 mL of ethyl acetate, and the reaction solvent was removed by rotary evaporation. The purified product was obtained by rapid column chromatography (stationary phase: 200–300 mesh silica gel; mobile phase: petroleum ether), with a yield of 92%. The synthetic route is as follows:

[0079]

[0080] (2) Preparation of benzylsilane compounds containing ortho-boron pinacol ester:

[0081] Take (4-(1-(dimethylsilyl)ethyl)phenyl)trimethylsilane (47.2 mg, 0.2 mmol, 1.0 equiv.), pinacol diboronate (152.4 mg, 0.6 mmol, 3.0 equiv.), and tri(methyl)phosphine (20 μL, 0.02 mmol, 1.0 M). In THF), bis(trimethylsilyl)amino potassium (8.0 mg, 0.04 mmol), bis-(1,5-cyclooctadiene)nickel (5.5 mg, 0.02 mmol), and tetrahydrofuran 0.5 mL were added. The mixture was reacted under nitrogen protection at 80 °C for 12 h in a sealed container. After cooling, the solvent was recovered under reduced pressure. The solution was separated by column chromatography (stationary phase: 200-300 mesh silica gel; mobile phase: petroleum ether: ethyl acetate = 50:1) to obtain 45.1 mg of (4-(1-(dimethylsilyl)ethyl)-3-(4,4,5,5-tetramethyl-1,3,2-dioxoboronyl-2-yl)phenyl)trimethylsilane, yield 62%. The structural formula is:

[0082]

[0083] Its structure was confirmed by NMR analysis; 1 H NMR(400MHz,Chloroform-d)δ7.89(d,J=2Hz,1H),7.51(dd,J=8,2Hz,1H),7.13(d,J=8Hz,1H),3.81–3.74(m,1H), 3.32(qd,J=8,2Hz,1H),1.38(d,J=8Hz,3H),1.34(s,12H),0.26(s,9H),0.01(d,J=4Hz,3H),-0.01(d,J=4Hz,3H). 13C{H}NMR(101MHz,Chloroform-d)δ153.6,141.0,136.0,134.1,124.7,83.2,25.2,25.0,24.8,15.0,-1.0,-5.2,-6.4.

[0084] Example 8

[0085] The method for preparing nickel-catalyzed benzylsilane compounds containing ortho-boronic acid pinacol esters according to the present invention includes the following steps:

[0086] (1) Preparation of dimethyl(1-naphthylmethyl)silane:

[0087] Magnesium powder (1.10 g, 45.8 mmol), THF (7.0 mL), dichloromethylsilane (5.0 mL, 45.0 mmol), and elemental iodine (5–10 grains) were added to a dry 100 mL three-necked round-bottom flask (equipped with a magnetic stir bar, reflux condenser, and constant-pressure dropping funnel). Then, 1-chloromethylnaphthalene (2.3 g, 13.0 mmol) was slowly added dropwise to the flask, and the reaction mixture was heated to reflux. After two hours of reaction, the reaction mixture was cooled to room temperature, and TLC analysis confirmed complete consumption of benzyl chloride. After the reaction was complete, the reaction mixture was diluted with 50 mL of petroleum ether, filtered, and washed with petroleum ether to obtain the reaction mixture. The reaction solvent was removed by rotary evaporation, and the purified product (stationary phase: 200–300 mesh silica gel; mobile phase: petroleum ether) was obtained by rapid column chromatography in 87% yield. The synthetic route is as follows:

[0088]

[0089] (2) Preparation of benzylsilane compounds containing ortho-boron pinacol ester:

[0090] Prepare dimethyl(1-naphthylmethyl)silane (40.0 mg, 0.2 mmol, 1.0 equiv.), pinacol diboronate (152.4 mg, 0.6 mmol, 3.0 equiv.), and tri(methyl)phosphine (20 μL, 0.02 mmol, 1.0 M in). THF), bis(trimethylsilyl)aminopotassium (8.0 mg, 0.04 mmol), bis-(1,5-cyclooctadiene)nickel (5.5 mg, 0.02 mmol), tetrahydrofuran 0.5 mL, under nitrogen protection, sealed at 80 °C for 12 h, cooled, solvent recovered under reduced pressure, and separated by column chromatography (stationary phase: 200-300 mesh silica gel, mobile phase: petroleum ether: ethyl acetate = 50:1) to obtain 40.4 mg of dimethyl((2-(4,4,5,5-tetramethyl-1,3,2-dioxoboronyl-2-yl)naphth-1-yl)methyl)silane, yield 62%), with the following structural formula:

[0091]

[0092] Its structure was confirmed by NMR analysis; 1 H NMR(400MHz,Chloroform-d)δ8.14–8.09(m,1H),7.84(d,J=8Hz,1H),7.81–7.78(m,1H),7.58(d,J=8 Hz,1H),7.50–7.45(m,2H),4.08–3.98(m,1H),3.18(d,J=4Hz,2H),1.39(s,12H),0.06(d,J=4Hz,6H). 13 C{H}NMR(101MHz,Chloroform-d)δ146.5,135.2,131.9,131.6,128.4,126.4,125.5,125.0,123.7,83.5,25.0,19.9,-3.7.

[0093] Example 9

[0094] The method for preparing nickel-catalyzed benzylsilane compounds containing ortho-boronic acid pinacol esters according to the present invention includes the following steps:

[0095] (1) Preparation of diethyl(1-(naphth-2-yl)ethyl)silane:

[0096] In a glove box, 2-vinylnaphthalene (308 mg, 2.0 mmol) and Et₂SiH₂ (616 mg, 7.0 mmol) were added to a 10.0 mL reaction tube. Subsequently, ultradry THF (1.0 mL) and KO₂ were added to the reaction mixture. t Bu (0.4 mmol). The reaction mixture was heated to 80 °C and reacted for 48 hours, then cooled to room temperature. The reaction mixture was diluted with 10.0 mL of ethyl acetate, the reaction solvent was removed by rotary evaporation, and the purified product was obtained by rapid column chromatography (stationary phase: 200-300 mesh silica gel; mobile phase: petroleum ether), with a yield of 83%. The synthetic route is as follows:

[0097]

[0098] (2) Preparation of benzylsilane compounds containing ortho-boron pinacol ester:

[0099] Take diethyl(1-(naphthyl-2-yl)ethyl)silane (42.8 mg, 0.2 mmol, 1.0 equiv.), pinacol diboronate (152.4 mg, 0.6 mmol, 3.0 equiv.), and tri(methyl)phosphine (20 μL, 0.02 mmol, 1.0 M in). THF), bis(trimethylsilyl)aminopotassium (8.0 mg, 0.04 mmol), bis-(1,5-cyclooctadiene)nickel (5.5 mg, 0.02 mmol), tetrahydrofuran 0.5 mL, under nitrogen protection, sealed at 80 °C for 12 h, cooled, solvent recovered under reduced pressure, and separated by column chromatography (stationary phase: 200-300 mesh silica gel, mobile phase: petroleum ether: ethyl acetate = 50:1) to obtain diethyl(1-(3-(4,4,5,5-tetramethyl-1,3,2-dioxoboronyl-2-yl)naphthyl)ethyl)silane 47.9 mg, yield 65%, structural formula:

[0100]

[0101] Its structure was confirmed by NMR analysis; 1 H NMR(400MHz,Chloroform-d)δ8.34(s,1H),7.82(d,J=8Hz,1H),7.74(d,J=8Hz,1H),7.55(s,1H),7.46(ddd,J=8,7,1Hz,1H),7.36(ddd,J=8,7,1Hz,1H) ,3.68–3.61(m,1H),3.52(qd,J=8,2Hz,1H),1.52(d,J=8Hz,3H),1.40(s,6H ),1.39(s,6H),0.92(t,J=8Hz,3H),0.91(t,J=8Hz,3H),0.69–0.47(m,3H). 13 C{H}NMR(101MHz,Chloroform-d)δ149.0,137.5,135.2,130.4,128.2,126.9,126.9,124.4,123.1,83.5,25.0,24.9,23.6,16.0,8.4,8.2,2.5,1.0.

[0102] Example 10

[0103] The method for preparing nickel-catalyzed benzylsilane compounds containing ortho-boronic acid pinacol esters according to the present invention includes the following steps:

[0104] (1) Preparation of dimethyl(pyrene-1-ylmethyl)silane:

[0105] Under anhydrous and oxygen-free conditions, magnesium powder (171 mg, 7.0 mmol), THF (5.0 mL), dichloromethylsilane (659 mg, 7.0 mmol), and elemental iodine (5–10 grains) were added to a dry 100 mL three-necked round-bottom flask (equipped with a magnetic stir bar, reflux condenser, and constant-pressure dropping funnel). Then, 1-chloromethylpyrene (0.5 g, 2.0 mmol) was slowly added dropwise to the flask, and the reaction mixture was heated to reflux. After two hours of reaction, the reaction mixture was cooled to room temperature, and TLC analysis confirmed complete consumption of benzyl chloride. After the reaction was complete, the reaction mixture was diluted with 50 mL of petroleum ether, filtered, and washed with petroleum ether to obtain the reaction mixture. The reaction solvent was removed by rotary evaporation, and the purified product (stationary phase: 200–300 mesh silica gel; mobile phase: petroleum ether) was obtained by rapid column chromatography in 51% yield. The synthetic route is as follows:

[0106]

[0107] (2) Preparation of benzylsilane compounds containing ortho-boron pinacol ester:

[0108] Prepare dimethyl(pyrene-1-ylmethyl)silane (54.8 mg, 0.2 mmol, 1.0 equiv.), pinacol diboronate (152.4 mg, 0.6 mmol, 3.0 equiv.), and tri(methyl)phosphine (20 μL, 0.02 mmol, 1.0 M in). THF), bis(trimethylsilyl)aminopotassium (8.0 mg, 0.04 mmol), bis-(1,5-cyclooctadiene)nickel (5.5 mg, 0.02 mmol), tetrahydrofuran 0.5 mL, under nitrogen protection, sealed at 80 °C for 12 h, cooled, solvent recovered under reduced pressure, and separated by column chromatography (stationary phase: 200-300 mesh silica gel, mobile phase: petroleum ether: ethyl acetate = 50:1) to obtain 40.4 mg of dimethyl((2-(4,4,5,5-tetramethyl-1,3,2-dioxoboronyl-2-yl)pyrene-1-yl)methyl)silane, yield 50%), with the following structural formula:

[0109]

[0110] Its structure was confirmed by NMR analysis; 1 H NMR(400MHz,Chloroform-d)δ8.64(s,1H),8.31(d,J=9Hz,1H),8.14–8.06(m,2H),8.08–8.00(m, 2H), 8.00–7.90 (m, 2H), 4.13–4.03 (m, 1H), 3.43 (d, J = 4Hz, 2H), 1.46 (s, 12H), 0.08 (d, J = 4Hz, 6H). 13C{H}NMR(101MHz,Chloroform-d)δ142.7,133.3,132.2,131.5,128.0,127.6,127. 5,126.7,126.3,126.2,125.7,124.9,124.7,124.3,124.1,83.8,25.0,20.6,-3.8.

[0111] Example 11

[0112] The method for preparing nickel-catalyzed benzylsilane compounds containing ortho-boronic acid pinacol esters according to the present invention includes the following steps:

[0113] (1) Preparation of (4-(((1R,2S,5R)-2-isopropyl-5-methylcyclohexyl)oxy)benzyl)dimethylsilane:

[0114] Under anhydrous and oxygen-free conditions, magnesium powder (367 mg, 15.8 mmol), THF (5.0 mL), dichloromethylsilane (1.5 g, 15.8 mmol), and elemental iodine (5-10 grains) were added to a dry 100 mL three-necked round-bottom flask (equipped with a magnetic stir bar, reflux condenser, and constant-pressure dropping funnel). Then, 1-(chloromethyl)-4-(((1R,2S,5R)-2-isopropyl-5-methylcyclohexyl)oxy)benzene (1.26 g, 4.5 mmol) was slowly added dropwise to the flask, and the reaction mixture was heated to reflux. After reacting for two hours, the reaction mixture was cooled to room temperature, and TLC analysis confirmed complete consumption of benzyl chloride. The reaction mixture was diluted with 50 mL of petroleum ether, filtered, and washed with petroleum ether to obtain the reaction mixture. The solvent was removed by rotary evaporation, and the purified product was obtained by rapid column chromatography (stationary phase: 200-300 mesh silica gel; mobile phase: petroleum ether), with a yield of 67%. The synthetic route is as follows:

[0115]

[0116] (2) Preparation of benzylsilane compounds containing ortho-boron pinacol ester:

[0117] Take (4-(((1R,2S,5R)-2-isopropyl-5-methylcyclohexyl)oxy)benzyl)dimethylsilane (60.8 mg, 0.2 mmol, 1.0 equiv.), pinacol diboronate (152.4 mg, 0.6 mmol, 3.0 equiv.), and tri(methyl)phosphine (20 μL, 0.02 mmol, 1.0 M in). THF), bis(trimethylsilyl)aminopotassium (8.0 mg, 0.04 mmol), bis-(1,5-cyclooctadiene)nickel (5.5 mg, 0.02 mmol), tetrahydrofuran 0.5 mL, under nitrogen protection, sealed at 80 °C for 12 h, cooled, solvent recovered under reduced pressure, separated by column chromatography (stationary phase: 200-300 mesh silica gel, mobile phase: petroleum ether: ethyl acetate = 20:1) to obtain (4-(((1R,2S,5R)-2-isopropyl-5-methylcyclohexyl)oxy)-2-(4,4,5,5-tetramethyl-1,3,2-dioxoboron-2-yl)benzyl)dimethylsilane 46.5 mg, yield 54%, structural formula:

[0118]

[0119] Its structure was confirmed by NMR analysis; 1 H NMR(400MHz,Chloroform-d)δ7.29(d,J=3Hz,1H),6.92(d,J=8Hz,1H),6.83(dd,J=8,3Hz,1H),4.62–4.55(m,1H),3.90–3.82(m,1H),2.48(d,J=3Hz,2H), 2.13–2.06(m,1H),1.80–1.50(m,6H),1.33(s,12H),1.06–0.94(m,2H),0.92 (d,J=7Hz,3H),0.87(d,J=6Hz,3H),0.80(d,J=6Hz,3H),0.04(d,J=4Hz,6H). 13 C{H}NMR(101MHz,Chloroform-d)δ154.4,138.7,129.6,123.5,117.7,83.3, 72.7,47.9,37.7,35.1,29.2,26.1,24.9,24.8,22.9,22.3,21.1,21.0,-4.4.

[0120] Example 12

[0121] The method for preparing nickel-catalyzed benzylsilane compounds containing ortho-boronic acid pinacol esters according to the present invention includes the following steps:

[0122] (1) Preparation of (4R)-4-(4-(1-(diethylsilyl)ethyl)benzyl)-2,2-dimethyloxazolidine-3-carboxylic acid tert-butyl ester:

[0123] In a glove box, (R)-2,2-dimethyl-4-(4-vinylbenzyl)oxazolidine-3-carboxylic acid tert-butyl ester (634 mg, 2.0 mmol) and Et2SiH2 (616 mg, 7 mmol) were added to a 10.0 mL reaction tube. Then, ultra-dry tetrahydrofuran (1.0 mL) and KO were added to the reaction mixture. t Bu (44.8 mg, 0.4 mmol). The reaction mixture was heated to 80 °C and reacted for 48 hours, then cooled to room temperature. The reaction mixture was diluted with 10.0 mL of ethyl acetate. The reaction solvent was removed by rotary evaporation, and the desired product was purified by rapid column chromatography (stationary phase: 200–300 mesh silica gel; mobile phase: petroleum ether). The product yield was 56%. The synthetic route is as follows:

[0124]

[0125] (2) Preparation of benzylsilane compounds containing ortho-boron pinacol ester:

[0126] Take (4R)-4-(4-(1-(diethylsilyl)ethyl)benzyl)-2,2-dimethyloxazolidine-3-carboxylic acid tert-butyl ester (81.0 mg, 0.2 mmol, 1.0 equiv.), pinacol diboronate (152.4 mg, 0.6 mmol, 3.0 equiv.), and tri(methyl)phosphine (20 μL, 0.02 mmol, 1.0 M in). THF), bis(trimethylsilyl)aminopotassium (8.0 mg, 0.04 mmol), bis-(1,5-cyclooctadiene)nickel (5.5 mg, 0.02 mmol), tetrahydrofuran 0.5 mL, under nitrogen protection, sealed at 80 °C for 12 h, cooled, solvent recovered under reduced pressure, separated by column chromatography (stationary phase: 200-300 mesh silica gel, mobile phase: petroleum ether: ethyl acetate = 10:1) to obtain (4R)-4-(4-(1-(diethylsilyl)ethyl)-3-(4,4,5,5-tetramethyl-1,3,2-dioxoboronyl-2-yl)benzyl)-2,2-dimethyloxazolidine-3-carboxylic acid tert-butyl ester 52 mg, yield 49%, structural formula:

[0127]

[0128] Its structure was confirmed by NMR analysis; 1H NMR(400MHz,Chloroform-d)δ7.65–7.58(m,1H),7.19–7.07(m,2H),4.16–3.94(m,1H),3.81–3.69(m,2H),3.59–3.50(m,1H),3. 40–3.28(m,1H),3.22–2.97(m,1H),2.67–2.55(m,1H),1.70–1.34(m,18H),1.32(s,12H),0.96–0.79(m,6H),0.63–0.41(m,4H). 13 C{H}NMR (101MHz, Chloroform-d): δ151.6,151.4,137.2,137.1,136.8,136.7,133.3,133.2,132.2,131.7,126.1,93.9,93.5,83 .4,83.3,80.0,79.6,66.2,65.8,59.5,59.0,39.2,37.8,28.6,28.3,27.6,26.9,24.9,23.3,23.1,16.1,8.3,8.1,2.2,1.2,1.2.

[0129] Example 13

[0130] The method for preparing nickel-catalyzed benzylsilane compounds containing ortho-boronic acid pinacol esters according to the present invention includes the following steps:

[0131] (1) Preparation of dimethyl(4-(((3aR,5R,5aS,8aS,8bR)-2,2,7,7-tetramethyltetrahydro-5H-bis([1,3]dioxanepentyl)[4,5-b:4',5'-d]pyran-5-yl)methoxy)benzyl)silane:

[0132] Under anhydrous and oxygen-free conditions, magnesium powder (183 mg, 7.3 mmol), THF (5.0 mL), dichlorodimethylsilane (687 mg, 7.3 mmol), and iodine (5–10 grains) were added to a dry 100 mL three-necked round-bottom flask (equipped with a magnetic stir bar, reflux condenser, and constant-pressure dropping funnel). Then, 2-(2-(chloromethyl)-5-(((3aR,5R,5aS,8aS,8bR)-2,2,7,7-tetramethyltetrahydro-5H-bis([1,3]dioxacyclopentene)[4,5-b:4',5'-d]pyran-5-yl)methoxy)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxoborane (806 mg, 2.1 mmol) was slowly added dropwise to the three-necked round-bottom flask, and the reaction mixture was heated to reflux. After reacting for two hours, the reaction mixture was cooled to room temperature, and TLC analysis confirmed complete consumption of benzyl chloride. After the reaction was complete, the reaction mixture was diluted with 50 mL of petroleum ether, filtered, and washed with petroleum ether to obtain the reaction mixture. The solvent was removed by rotary evaporation, and the purified product was obtained by rapid column chromatography (stationary phase: 200–300 mesh silica gel; mobile phase: petroleum ether), with a yield of 61%. The synthetic route is as follows:

[0133]

[0134] (2) Preparation of benzylsilane compounds containing ortho-boron pinacol ester:

[0135] Take dimethyl(4-(((3aR,5R,5aS,8aS,8bR)-2,2,7,7-tetramethyltetrahydro-5H-bis([1,3]dioxanepentyl)[4,5-b:4',5'-d]pyran-5-yl)methoxy)benzyl)silane (40.8 mg, 0.1 mmol, 1.0 equiv.), pinacol diboronate (76.2 mg, 0.3 mmol, 3.0 equiv.), and tri(methyl)phosphine (10 μL, 0.01 mmol, 1.0 M). In THF), potassium bis(trimethylsilyl)amino (4.0 mg, 0.02 mmol), nickel trifluoromethanesulfonate (3.6 mg, 0.01 mmol), and tetrahydrofuran (0.5 mL) were added. The mixture was reacted at 80 °C for 12 h under nitrogen protection and sealed. After cooling, the solvent was recovered under reduced pressure. The solution was separated by column chromatography (stationary phase: 200-300 mesh silica gel; mobile phase: petroleum ether: ethyl acetate = 5:1) to obtain 29.9 mg of dimethyl(2-(4,4,5,5-tetramethyl-1,3,2-dioxoboronyl-2-yl)-4-(((3aR,5R,5aS,8aS,8bR)-2,2,7,7-tetramethyltetrahydro-5H-bis([1,3]dioxoboronyl)[4,5-b:4',5'-d]pyran-5-yl)methoxy)benzyl)silane, yield: 56%). The structural formula is:

[0136]

[0137] Its structure was confirmed by NMR analysis; 1 H NMR(400MHz,Chloroform-d)δ7.35(d,J=2Hz,1H),6.95–6.89(m,2H),5.56(d,J=5Hz,1H),4.64(dd,J=8,2Hz,1H),4.38(dd,J=8,1Hz,1H),4.33(dd,J=5,2 Hz,1H),4.21–4.08(m,3H),3.88–3.78(m,1H),2.49(d,J=2Hz,2H),1.51(s,3 H),1.47(s,3H),1.36(s,3H),1.34(s,3H),1.32(s,12H),0.02(d,J=4Hz,6H). 13 C{H}NMR(101MHz,Chloroform-d)δ154.8,139.8,129.7,121.8,117.9,109.3,108.7,96.4 ,83.3,70.9,70.7,70.6,66.3,66.1,26.1,26.0,25.0,24.9,24.9,24.4,22.9,-4.5,-4.5.

[0138] Example 14

[0139] The method for preparing nickel-catalyzed benzylsilane compounds containing ortho-boronic acid pinacol esters according to the present invention includes the following steps:

[0140] (1) Preparation of (4-(((3R,5S,8R,9S,10S,13R,14S)-10,13-dimethyl-17-((R)-6-methylheptane-2-yl)hexadecylhydro-1H-cyclopentano[a]phenanthrene-3-yl)oxy)benzyl)dimethylsilane:

[0141] Under anhydrous and oxygen-free conditions, magnesium powder (147 mg, 7.1 mmol), THF (5.0 mL), dimethylchlorosilane (0.6 g, 7.0 mmol), and elemental iodine (5–10 grains) were added to a dry 100 mL three-necked round-bottom flask (equipped with a magnetic stir bar, reflux condenser, and constant-pressure dropping funnel). Then, (3R,5S,8R,9S,10S,13R,14S)-3-(4-(chloromethyl)phenoxy)-10,13-dimethyl-17-((R)-6-methylheptane-2-yl)hexadechydro-1H-cyclopenta[a]phenanthrene (1.02 g, 2.0 mmol) was slowly added dropwise to the flask, and the reaction mixture was heated to reflux. After two hours of reaction, the reaction mixture was cooled to room temperature, and TLC analysis confirmed complete consumption of benzyl chloride. After the reaction was complete, the reaction mixture was diluted with 50 mL of petroleum ether, then filtered, and washed with petroleum ether to obtain the reaction mixture. The reaction solvent was removed by rotary evaporation, and the purified product was obtained by rapid column chromatography (stationary phase: 200-300 mesh silica gel; mobile phase: petroleum ether), with a yield of 58%.

[0142]

[0143] (2) Preparation of benzylsilane compounds containing ortho-boron pinacol ester:

[0144] Take (4-(((3R,5S,8R,9S,10S,13R,14S)-10,13-dimethyl-17-((R)-6-methylheptane-2-yl)hexadecylhydro-1H-cyclopenta[a]phenanthrene-3-yl)oxy)benzyl)dimethylsilane (53.6 mg, 0.1 mmol, 1.0 equiv.), pinacol diboronate (76.2 mg, 0.3 mmol, 3.0 equiv.), and tri(methyl)phosphine (10 μL, 0.01 mmol, 1.0 M). In THF, bis(trimethylsilyl)aminopotassium (4.0 mg, 0.02 mmol), bis-(1,5-cyclooctadiene)nickel (2.8 mg, 0.01 mmol), and tetrahydrofuran 0.5 mL were added. The mixture was reacted under nitrogen protection at 80 °C for 12 h, then cooled and the solvent was recovered under reduced pressure. The mixture was then separated by column chromatography (stationary phase: 200-300 mesh silica gel; mobile phase: petroleum ether: ethyl acetate = 10:1). 32.4 mg of (4-(((3R,5S,8R,9S,10S,13R,14S)-10,13-dimethyl-17-((R)-6-methylheptane-2-yl)hexadecylhydro-1H-cyclopenta[a]phenanthrene-3-yl)oxy)-2-(4,4,5,5-tetramethyl-1,3,2-dioxoborhecyclopentane-2-yl)benzyl)dimethylsilane was obtained in 49% yield, with the following structural formula:

[0145]

[0146] Its structure was confirmed by NMR analysis; 1 H NMR(400MHz,Chloroform-d)δ7.31(d,J=3Hz,1H),6.91(d,J=8Hz,1H),6.84(dd,J=8,3Hz, 1H),4.52–4.47(m,1H),3.90–3.80(m,1H),2.48(d,J=3Hz,2H),1.97(dt,J=12,3Hz,1H),1 .91–1.75(m,2H),1.70–1.42(m,13H),1.32(s,12H),1.28–0.98(m,15H),0.91(d,J=6Hz,3 H),0.87(d,J=7Hz,3H),0.87(d,J=7Hz,3H),0.81(s,3H),0.65(s,3H),0.03(d,J=4Hz,6H). 13 C{H}NMR (101MHz, Chloroform-d): δ154.0,139.1,129.6,123.7,118.7,83.3,72.0,56.5,56.2,54.1,42.6,40.1,39.5,36.2,35 .8,35.8,35.5,32.9,32.7,32.0,28.5,28.3,28.0,25.7,24.9,24.9,24.2,23.8,22.9,22.8,22.6,20.8,18.7,12.1,11.4,-4.4.

Claims

1. A method for producing a nickel-catalyzed benzylic silyl compound containing a pinacol ester of ortho-boric acid, characterized by, The benzyl silane compound and pinacol diboron are used as raw materials, and a benzyl silane compound containing an ortho borate is obtained by reaction in a catalytic system of an organic nickel catalyst, a phosphine ligand and a base, and the synthesis route is as follows:

2. The method for producing a nickel-catalyzed benzylsilane compound containing a pinacol ester of ortho-boric acid according to claim 1, characterized by, R is selected from H, C1-C3alkyl; R 1 R is selected from H, C1-C3alkyl; R 3 R is selected from H, C1-C3alkyl; R 3 R is selected from H, C1-C3alkyl; R 3. The method for preparing a nickel-catalyzed benzylic silylboronate compound according to claim 1, characterized by, The reaction temperature is 50-100 ℃.

4. The method for preparing a nickel-catalyzed benzylic silylboronate compound according to claim 1, characterized by, The molar ratio of the benzyl silane compound to pinacol diboron is 1:2-4.

5. The method for preparing a nickel-catalyzed benzylic silylboronate compound according to claim 1, characterized by, The molar ratio of the base, the phosphine ligand, the organic nickel catalyst is =1:2-4:0.1-0.2:0.05-0.10:0.05-0.

10.

6. The method for preparing a nickel-catalyzed benzylic silylboronate compound according to claim 1, characterized by, The organic nickel catalyst is bis-(1,5-cyclooctadiene)nickel or nickel triflate.

7. The method for preparing a nickel-catalyzed benzylic silylboronate compound according to claim 1, characterized by, The phosphine ligand is selected from one or more of tri(methyl)phosphine, tri(ethyl)phosphine, tri(cyclohexyl)phosphine, tri(n-butyl)phosphine and tri(tert-butyl)phosphine.

8. The method for preparing a nickel-catalyzed benzylic silylboronate compound according to claim 1, characterized by, The solvent of the reaction is n-hexane, tetrahydrofuran or 2-methyltetrahydrofuran.

9. The method for preparing a nickel-catalyzed benzylic silylboronate compound according to claim 1, characterized by, The base is selected from one or more of sodium tert-butoxide, potassium tert-butoxide, sodium methoxide, potassium methoxide, potassium bis(trimethylsilyl)amide and sodium bis(trimethylsilyl)amide.

10. The method for preparing a nickel-catalyzed benzylic silylboronate compound according to claim 1, characterized by, The benzyl silane compound containing an ortho borate has the structural formula:

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