Silicon-containing chiral alkenyl silicon-hydrogen compound as well as preparation method and application thereof

Abstract

The invention discloses a silicon-containing chiral alkenyl silicon-hydrogen compound and a synthesis method thereof. The invention provides a silicon-containing chiral alkenyl silicon-hydrogen compound with a structural formula as shown in a formula (I) and a synthesis method for synthesizing the compound, and particularly comprises the following steps: adding a ligand and a palladium catalyst into a solvent for pre-stirring, and then reacting dihydrosilane with an alkyne substrate to obtain the compound as shown in the formula (I). According to the invention, novel ligands L1-L9 are adopted and have higher catalytic efficiency on asymmetric hydrosilylation reaction, the conversion number TON is equal to 29702, and the defect that the variety of traditional ligands is limited is overcome; the method disclosed by the invention is better in adaptability and can be suitable for various alkynyl compounds, such as alkyne reaction containing-N,-P and ether substituent groups; compared with the asymmetric hydrosilylation reaction reported in the literature, the enantiomeric excess of the alkenyl hydrosilylation compound in the synthesis method is high, and the maximum enantiomeric excess can reach 94% ee. # imgabs0 #

Description

Technical Field

[0001] The invention belongs to the field of organic synthesis, and particularly relates to a silicon-containing chiral alkenyl silicon hydride compound and a preparation method and application thereof. Background Art

[0002] Silicon-containing chiral alkenyl silicon hydrides have important application value in the fields of medicinal chemistry, materials science and organic synthesis due to their unique physical and chemical properties. With the vigorous development of asymmetric catalysis, transition metal-catalyzed hydrosilylation has become one of the most direct and efficient methods for synthesizing chiral organosilicon compounds, with the advantages of simple operation, high reaction efficiency and mild conditions. Although the research on asymmetric catalytic hydrosilylation has provided many effective strategies for the synthesis of carbon-containing organosilicon compounds in the past few decades. However, the following problems still exist: 1) The substrate adaptability is poor, and it can only react with simple phenyl-substituted and aliphatic substituted alkynyl compounds, and it is impossible to efficiently construct a variety of silicon-containing chiral alkenyl silicon hydrides containing heteroatoms (such as N and O heteroatoms). 2) The catalytic efficiency is poor and the enantiomeric excess is low.

[0003] Therefore, exploring a simple, effective, and asymmetric catalytic method that can be applied to a variety of heteroatom alkynes will be of research significance for the construction of chiral silicon hydrides and material synthesis. At the same time, the development of a variety of silicon-containing chiral alkenyl silicon hydrides has exploratory value for medicinal chemistry and material science.

[0004] In summary, it is necessary to construct a new strategy for silicon-containing chiral alkenyl silicon hydrides to construct a variety of silicon-containing chiral alkenyl silicon hydrides. Summary of the invention

[0005] The first object of the present invention is to provide a silicon-containing chiral alkenyl silicon hydride compound in view of the deficiencies in the prior art.

[0006] A silicon-containing chiral alkenyl silicon hydride compound, the chemical structure of which is shown in the following formula (I).

[0007] In formula (I), * represents chirality, which is R or S; R 1 for or , the dihydrosilane formed by this substituent has high enantioselectivity; R 2 , R 3 Each is independently selected from one of the following structures: Phenyl, , , , , , , , , , , , , , , , , , , .

[0008] Preferably, the chemical structural formula of the silicon-containing chiral alkenyl silicon hydride compound is selected from any one of the following Ia to It: The second object of the present invention is to provide a method for preparing the above-mentioned compound, which has strong adaptability and novel strategy.

[0009] A method for synthesizing a silicon-containing chiral alkenyl silicon hydride compound comprises the following steps: In the presence of a phosphine ligand, a palladium catalyst and a reaction medium, a dihydrosilane represented by formula (II) and an alkynyl compound represented by formula (III) are subjected to an asymmetric hydrosilylation reaction to synthesize a silicon-containing chiral alkenyl silicon hydride compound represented by formula (I). The reaction formula is shown below: Among them, R 1 for or ; R 2 , R 3 Independently selected from one of the following structures: Phenyl, , , , , , , , , , , , , , , , , , .

[0010] Preferably, the palladium catalyst is selected from Pd2(dba)3·CH3Cl, Pd2(dba) 3、Any one of Pd(OAc)2, Pd(cod)2Cl2, Pd(nbd)2Cl2, Pd(acac)2, more preferably Pd2(dba)3·CH3Cl, Pd2(dba)3; the palladium catalyst has high catalytic efficiency and can obtain the target product in high yield.

[0011] Preferably, the phosphine ligand is selected from one or more of the following compounds L1 to L9: More preferred are compounds L1, L2, L6 and L8; the complex formed by the palladium catalyst and the phosphine ligand is used as a catalyst with good catalytic efficiency and can obtain the target product with high yield and high enantioselectivity.

[0012] Preferably, the method is as follows: in an inert gas atmosphere, the phosphine ligand, the palladium catalyst, and the reaction medium are pre-stirred for 30 to 45 minutes, and then the dihydrosilane represented by formula (II) and the alkynyl compound represented by formula (III) are added in sequence, and the reaction is carried out at 0 to 40° C. for 2 to 18 hours to obtain a silicon-containing chiral alkenyl silicon hydride compound.

[0013] Preferably, the molar ratio of the dihydrosilane represented by formula (II), the alkynyl compound represented by formula (III), the palladium catalyst, and the phosphine ligand is 1:1:(0.001-0.003):(0.06-0.10).

[0014] Preferably, the reaction medium is any one of toluene, tetrahydrofuran, dichloromethane, n-hexane and cyclohexane, and more preferably tetrahydrofuran and cyclohexane.

[0015] Preferably, after the reaction is completed, a post-treatment step is further included; the post-treatment includes: removing the solvent by rotary evaporation, and separating and purifying the crude product by silica gel column chromatography.

[0016] The third object of the present invention is to provide an application of a silicon-containing chiral alkenyl silicon hydride compound in the preparation of a silicon-containing chiral drug or an organic photoelectric functional material.

[0017] In the silicon-containing chiral alkenyl silicon hydride compound provided by the present invention, the product Io has a condensed ring structure and has 87% ee, and can be applied in optoelectronic materials. The product Ir has an alkyne amide structure and can be applied in molecular probes.

[0018] Compared with the prior art, the present invention has the following advantages: 1. The preparation method used in the present invention is simple to operate, does not require water and oxygen removal operations, and can be reacted in a state of complete exposure to air, overcoming the defect that the prior art needs to implement silicon chiral construction under strict anhydrous and oxygen-free conditions. In addition, the silicon-containing chiral alkenyl silicon hydride prepared by the method of the present invention has a high enantiomeric excess, which can reach up to 94% ee and 90% yield.

[0019] 2. In the hydrosilylation reactions reported so far, many traditional ligands are used. The present invention uses new ligands L1 to L9, which have higher catalytic efficiency for asymmetric hydrosilylation reactions, with a turnover number of TON = 29702, and are insensitive to water and oxygen, and can be used for industrial production.

[0020] 3. Traditional hydrosilylation reactions lack the silicon chiral construction for heteroatom alkynes and can only react with simple benzynes and aliphatic alkynes. The adaptability of the present invention is better and can be applied to a variety of acetylenic compounds, such as alkynes containing -N and ether substituents, and most of them can reach 90% ee.

[0021] 4. The product of the present invention has a polycyclic or amide structure and has good applicability in optoelectronic materials and molecular probe materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 is the H NMR spectrum of the silicon-containing chiral alkenyl silicon hydride compound prepared in Example 1; Figure 2 is the NMR carbon spectrum of the silicon-containing chiral alkenyl silicon hydride compound prepared in Example 1; Figure 3 is the H NMR spectrum of the silicon-containing chiral alkenyl silicon hydride compound prepared in Example 2; Figure 4 is the NMR carbon spectrum of the silicon-containing chiral alkenyl silicon hydride compound prepared in Example 2; Figure 5 is the H NMR spectrum of the silicon-containing chiral alkenyl silicon hydride compound prepared in Example 3; Figure 6 The NMR carbon spectrum of the silicon-containing chiral alkenyl silicon hydride compound prepared in Example 3; Figure 7 is the H NMR spectrum of the silicon-containing chiral alkenyl silicon hydride compound prepared in Example 4; Figure 8 This is the NMR carbon spectrum of the silicon-containing chiral alkenyl silicon hydride compound prepared in Example 4. DETAILED DESCRIPTION

[0023] The present invention is further described in detail below with reference to the examples. The raw materials used in the examples can be purchased from the market or prepared by conventional methods.

[0024] The present invention is to carry out conventional reactions under nitrogen protection and magnetic stirring conditions. The catalytic reaction is carried out in a 25mL Schlenk tube under nitrogen protection. Anhydrous cyclohexane, tetrahydrofuran, and dichloromethane solvents are obtained by an inert solvent purification system. TLC thin layer chromatography is performed on a Huanghai HSGF254 plate, and the developed chromatogram is developed by fluorescence quenching. Silica gel column chromatography is performed using GENERAR-REAGENT silica gel (200-300 g). Unless otherwise specified, all reagents are purchased from commercial suppliers and can be used directly without further purification. Nuclear magnetic resonance (NMR) spectra are recorded at ambient temperature using a Bruker DPX 400 or Bruker DPX 600 instrument. 1 H NMR (400 MHz), recorded 13 C NMR (100 MHz), recorded 19 F NMR (500 MHz). Chemical shifts (δ) are expressed in ppm and coupling constants (J) are expressed in Hertz (Hz). NMR standards used were as follows: ( 1 H NMR)CDCl3 =7.26ppm; ( 13 C NMR) CDCl3 =77.00 ppm. 1 H NMR data are recorded as follows: δ represents chemical shift, s represents singlet, d represents doublet, dd represents doublet of doublets, t represents triplet, q represents quartet, m represents multiplet, br represents broad peak, and coupling constant is in Hz. 13 C NMR. Chiral HPLC chromatograms were recorded using an ultra-high performance liquid chromatography series, λ=254nm, and a temperature of 20°C. High resolution mass spectra (HRMS) were recorded on an Agilent Technologies 6230TOF LC / MS under electrospray ionization (ESI) conditions using CH3OH as solvent. Optical rotations were measured on a SGW-533 automatic polarimeter, and the sample concentration in CHCl3 was 1.0.

[0025] Embodiment 1: First, 0.5 mol% Pd2(dba)3·CH3Cl and 4 mol% ligand L1 were weighed into a Schlenk tube and replaced with N2 three times. Cyclohexane was added and pre-stirred for 30 minutes. Then 45.2 mg dihydrosilane and 41.2 mg Ⅲa were added and stirred at 0°C for 6 hours. Then, the alkenylsilane product Ⅰa was obtained by silica gel column chromatography (PE: EA = 50: 1), which was a yellow viscous oil (69.3 mg, 80% yield), 92% ee. HPLC conditions: using an ultra-high performance liquid chromatography MD (Guangzhou Pheromon Scientific Instrument Co., Ltd.) column (n-hexane / isopropanol = 99.9:0.1, 0.5 mL / min), λ = 254 nm, temperature = 20 °C, the elution time of the minor enantiomer was 7.83 minutes, the elution time of the major enantiomer was 10.33 minutes, [α] D 20 = 58.2 (c = 1.04, CHCl3). 1 HNMR (400 MHz, CDCl3): δ 7.50 (d, J = 1.5 Hz, 1H),7.50 (d, J = 1.5 Hz, 1H) 7.34-7.28 (m, 2H), 7.22 (s, 1H), 7.00-6.95 (m, 4H),6.89-6.84 (m, 5H), 6.81 (s, 2H), 5.49 (s, 1H), 2.29 (s, 6H) 2.60 (s, 3H), 2.26 (s, 3H), 2.20 (s, 3H). 13 C NMR (100 MHz, CDCl3) δ 145.7, 142.0, 139.9, 139.3,139.1, 137.3, 135.9, 135.7, 134.7, 134.5, 129.6, 129.5, 129.4, 128.9, 128.8,128.02, 127.95, 127.1, 31.7, 30.3, 24.6, 21.4.

[0026] HRMS (ESI): Accurate mass calculation C 31 H 32 Si [M+Na + ]:455.2165 , measured value 455.2162.

[0027] The H NMR spectrum of compound Ia is shown in Figure 1 As shown, the NMR carbon spectrum is as follows Figure 2 shown.

[0028] Embodiment 2: First, 1 mol% Pd2(dba)3 and 6 mol% ligand L2 were weighed into a Schlenk tube and replaced with N2 three times. Dichloromethane was added and pre-stirred for 40 minutes. Then 45.2 mg dihydrosilane and 52.4 mg Ⅲb were added and stirred at 20°C for 1 hour. Then, the alkenylsilane product Ⅰb was obtained by silica gel column chromatography (PE: EA = 50: 1), which was a yellow viscous oil (71.8 mg, 74% yield), 94% ee. HPLC conditions: using an ultra-high performance liquid chromatography MD (Guangzhou Pheromon Scientific Instrument Co., Ltd.) column (n-hexane / isopropanol = 99.9:0.1, 0.5 mL / min), λ = 254 nm, temperature = 20 °C, the elution time of the minor enantiomer was 5.13 minutes, the elution time of the major enantiomer was 7.50 minutes, [α] D 20 =38.0 (c = 1.47, CHCl3). . 1 H NMR (400 MHz, CDCl3): δ 7.55 (d, J = 1.6 Hz, 1H), 7.53 (d, J = 1.6 Hz, 1H), 7.37-7.31 (m, 3H), 7.12 (d, J = 8.2 Hz, 2H), 7.07(d, J = 8.3Hz, 2H), 7.00(m, 4H), 6.90 (s, 1H), 6.87 (s, 2H), 5.54 (s, 1H),2.91(dt, J = 56.6, 6.4 Hz, 2H), 2.33 (s, 6H), 2.32 (s, 3H), 1.26 (d, J = 6.8Hz, 6H), 1.20 (d, J =7.0 Hz, 6H). 13 C NMR (101 MHz, CDCl3) δ 148.3, 146.8,145.8, 141.9, 139.8, 139.7, 139.2, 135.9, 135.0, 134.6, 129.8, 129.3, 128.9,128.0, 127.9, 127.1, 126.9, 126.1, 33.9, 33.9, 24.6, 24.2, 24.2, 23.97,23.95, 21.4.

[0029] HRMS (ESI): Accurate mass calculation C 31 H32 Si [M+Na + ]:455.2165 , measured value 455.2162.

[0030] The H NMR spectrum of compound IIa is shown in Figure 3 As shown, the NMR carbon spectrum is as follows Figure 4 shown.

[0031] Embodiment 3: First, 2 mol% Pd(OAc)2 and 8 mol% ligand L3 were weighed into a Schlenk tube and replaced with N2 three times. Dichloromethane was added and pre-stirred for 50 minutes. Then 45.2 mg dihydrosilane and 58.0 mg IIIc were added and stirred at 40°C for 8 hours. Then, the vinylsilane product Ic was obtained by silica gel column chromatography (PE: EA = 50: 1), which was a yellow viscous oil (70.0 mg, yield 62%), 91% ee. HPLC conditions: using an ultra-high performance liquid chromatography MD column (n-hexane / isopropanol = 99.9:0.1, 0.5 mL / min), λ = 254 nm, temperature = 20°C, the minor enantiomer peak time was 6.70 minutes, the major enantiomer peak time was 8.84 minutes, [α] D 20 = 6.8 (c = 0.85, CHCl3). 1 HNMR (400 MHz, CDCl3): δ 7.44 (d, J = 1.5 Hz, 1H), 7.42 (d, J = 1.6 Hz, 1H), 7.27-7.15 (m, 5H), 7.03 (d, J = 8.2Hz, 2H), 6.97 (d, J = 8.4 Hz, 2H), 6.86(d, J = 8.2 Hz, 2H), 6.80 (s, 1H), 6.76 (s, 2H), 5.54 (s, 1H), 2.22 (s, 6H), 2.20 (s, 3H), 1.22 (s, 6H), 1.15 (s, 6H). 13CNMR (100 MHz, CDCl3) δ 150.6,149.1, 145.8, 141.7, 139.8, 139.3, 139.2, 135.9, 134.6, 129.5, 129.3, 128.9,128.0, 127.5, 127.1, 125.7, 125.0, 34.7, 34.58, 31.55, 31.3, 24.6, 21.4.

[0032] HRMS (ESI): Accurate mass calculation C 37 H 44 Si [M+K + ]:555.2844 , measured value 555.2825.

[0033] The H NMR spectrum of compound IIIa is shown in Figure 5 As shown, the NMR carbon spectrum is as follows Figure 6 shown.

[0034] Embodiment 4: First, 4 mol% Pd(cod)2Cl2 and 12 mol% ligand L4 were weighed into a Schlenk tube and replaced with N2 three times. Then, n-hexane was added and pre-stirred for 60 minutes. Then, 45.2 mg dihydrosilane and 46.8 mg IIId were added and stirred at 60°C for 15 hours. Then, the alkenylsilane product Id was obtained by silica gel column chromatography (PE: EA = 50: 1), which was a yellow viscous oil (49.6 mg, 54% yield), 90% ee. HPLC conditions: using ultra-high performance liquid chromatography MD (Guangzhou Pheromon Scientific Instrument Co., Ltd.) column (n-hexane / isopropanol = 99.9:0.1, 0.5mL / min), λ = 254 nm, temperature = 20°C, the elution time of the minor enantiomer was 6.70 minutes, the elution time of the major enantiomer was 8.84 minutes, [α] D 20 = 6.8 (c = 0.85, CHCl3). 1H NMR (400 MHz, CDCl3): δ 7.57 (d, J = 1.6 Hz, 1H),7.55 (d, J = 1.6 Hz, 1H) 7.36-7.33 (m, 3H),7.08 (s, 4H), 6.96 (s, 4H), 6.92(s, 1H), 6.88 (s, 2H), 5.57 (s, 1H), 2.63 (q, J = 7.6 Hz, 2H), 2.56 (q, J =7.6 Hz, 2H), 2.36 (s, 6H) 2.32 (s, 3H), 1.26 (t, J = 7.6 Hz, 3H), 1.20 (t, J =7.6 Hz, 3H). 13 C NMR (101 MHz, CDCl3) δ 145.8, 143.7, 142.1, 142.0, 139.8,139.5, 139.2, 135.9, 135.0, 134.6, 129.8, 129.3, 128.9, 128.3, 128.01,127.97, 127.6, 127.2, 28.67, 28.65, 24.6, 21.4, 15.6, 15.4.

[0035] HRMS (ESI): Accurate mass calculation C 33 H 36 Si [M+Na + ]:483.2438 , measured value 483.2459.

[0036] The H NMR spectrum of compound IIIa is shown in Figure 7 As shown, the NMR carbon spectrum is as follows Figure 8 shown.

[0037] Embodiment 5: First, 2 mol% Pd(nbd)2Cl2 and 8 mol% ligand L5 were weighed into a Schlenk tube and replaced with N2 three times. Cyclohexane was added and pre-stirred for 30 minutes. Then 45.2 mg dihydrosilane and 42.8 mg IIIe were added and stirred at 0°C for 10 hours. Then, the alkenylsilane product Ie was obtained by silica gel column chromatography (PE: EA = 50: 1), which was a yellow viscous oil (86.4 mg, 97% yield), 91% ee. HPLC conditions: using ultra-high performance liquid chromatography MD (Guangzhou Pheromon Scientific Instrument Co., Ltd.) column (n-hexane / isopropanol = 99.9:0.1, 0.5mL / min), λ = 254 nm, temperature = 20°C, the elution time of the minor enantiomer was 6.86 minutes, the elution time of the major enantiomer was 7.69 minutes, [α] D 20 = 36.3 (c = 0.65, CHCl3). 1 H NMR (400 MHz, CDCl3): δ 7.43 (d, J = 1.6 Hz,1H), 7.42 (d, J = 1.2 Hz, 1H) 7.29-7.20 (m, 3H), 6.97-6.93 (m, 2H), 6.86-6.80(m, 5H), 6.76 (s, 2H), 6.70 (dd, J =8.8 Hz, 2H), 5.47 (s, 1H), 2.24 (s, 6H), 2.20 (s, 3H). 13 C NMR (101 MHz, CDCl3) δ 163.2, 162.9, 160.8, 160.4, 145.7,141.4, 140.2, 139.1, 137.7, 135.8, 133.7, 133.3, 131.4, 131.3, 129.7, 129.6,129.0, 128.2, 126.3, 116.0, 115.8, 115.2, 115.0, 24.6, 21.4.

[0038] HRMS (ESI): Accurate mass calculation C 33 H 36 Si [M+K + ]:579.1340 , measured value 579.1354.

[0039] Embodiment 6: First, 2 mol% Pd(acac)2 and 8 mol% ligand L6 were weighed into a Schlenk tube and replaced with N2 three times. Cyclohexane was added and pre-stirred for 30 minutes. Then 45.2 mg dihydrosilane and 62.8 mg IIIf were added and stirred at 80°C for 20 hours. Then, the vinylsilane product If was obtained by silica gel column chromatography (PE: EA = 50: 1), which was a yellow viscous oil (102.6 mg, yield 95%), 90% ee. HPLC conditions: using an ultra-high performance liquid chromatography MD column (n-hexane / isopropanol = 99.9:0.1, 0.5 mL / min), λ = 254 nm, temperature = 20°C, the minor enantiomer peak time was 9.65 minutes, the major enantiomer peak time was 11.60 minutes, [α] D 20 = 46.1 (c = 0.43,CHCl3). 1 H NMR (400 MHz, CDCl3): δ 7.45 (d, J = 1.2 Hz, 1H), 7.44 (d, J = 2.0Hz, 1H) 7.39 (d, J = 8.2 Hz, 2H), 7.29-7.22 (m, 5H), 7.09 (d, J = 8.0 Hz,2H), 6.95 (m, 3H), 6.79 (s, 2H), 5.49 (s, 1H), 2.26 (s, 6H), 2.21 (s, 3H). 13 CNMR (101 MHz, CDCl3) δ 145.7, 145.6, 142.7, 141.5, 140.6, 140.2, 135.9,132.9, 130.2, 129.8, 129.2, 128.3, 128.3, 126.0, 125.9, 125.6, 125.2, 125.2,125.2, 125.1, 77.5, 77.2, 76.9, 24.6, 21.4.

[0040] HRMS (ESI): Accurate mass calculation C 33 H 36 Si [M+K + ]:579.1340 , measured value 579.1354.

[0041] Embodiment 7: First, 2 mol% Pd2(dba)3·CH3Cl and 8 mol% ligand L7 were weighed into a Schlenk tube and replaced with N2 three times. Cyclohexane was added and pre-stirred for 30 minutes. Then 45.2 mg dihydrosilane and 49.2 mg IIIg were added and stirred at 100°C for 6 hours. Then, the alkenylsilane product Ig was obtained by silica gel column chromatography (PE: EA = 50: 1), which was a yellow viscous oil (79.3 mg, 84% yield), 92% ee. HPLC conditions: using ultra-high performance liquid chromatography MD (Guangzhou Pheromon Scientific Instrument Co., Ltd.) column (n-hexane / isopropanol = 99.9:0.1, 0.5mL / min), λ = 254 nm, temperature = 20°C, the elution time of the minor enantiomer is 9.76 minutes, the elution time of the major enantiomer is 12.74 minutes, [α] D 20 = 16.9 (c = 1.13, CHCl3). 1 H NMR (400 MHz, CDCl3): δ 7.45 (d, J = 1.6 Hz, 1H), 7.43 (d, J = 1.6 Hz, 1H) 7.38 (d, J = 8.2 Hz, 2H), 7.30-7.22 (m, 5H), 7.09 (d, J = 8.0 Hz, 2H), 6.95-6.93 (m, 3H), 6.78 (s, 2H), 5.49 (s, 1H), 2.25(s, 6H), 2.20 (s, 3H). 13 C NMR (101 MHz, CDCl3) δ 145.7, 145.6, 142.7, 141.5,140.6, 140.2, 135.9, 132.9, 130.0, 129.7, 129.2, 128.3, 128.3, 125.98,125.95, 125.9, 125.87, 125.6, 125.2, 125.2, 125.2, 125.1, 24.6, 21.4.

[0042] HRMS (ESI): Accurate mass calculation C 33 H 36 Si [M+] + :472.1175, measured value 472.1800.

[0043] Embodiment 8: First, 4 mol% Pd2(dba)3·CH3Cl and 12 mol% ligand L8 were weighed into a Schlenk tube and replaced with N2 three times. Cyclohexane was added and pre-stirred for 30 minutes. Then 45.2 mg dihydrosilane and 49.2 mg IIIh were added and stirred at 0°C for 30 hours. Then, the alkenylsilane product Ih was obtained by silica gel column chromatography (PE: EA = 50: 1), which was a yellow viscous oil (84.1 mg, 89% yield), 91% ee. HPLC conditions: using ultra-high performance liquid chromatography MD (Guangzhou Pheromon Scientific Instrument Co., Ltd.) column (n-hexane / isopropanol = 99.9:0.1, 0.5mL / min), λ = 254 nm, temperature = 20°C, the elution time of the minor enantiomer was 8.59 minutes, the elution time of the major enantiomer was 10.36 minutes, [α] D 20 = 37.2 (c = 1.65, CHCl3). 1 H NMR (400 MHz, CDCl3): δ 7.43 (d, J = 1.6 Hz, 1H), 7.42 (d, J = 2.0 Hz, 1H) 7.29-7.22 (m, 3H), 7.10 (d, J = 8.2 Hz, 2H), 6.99 (d, J = 8.2 Hz, 2H), 6.92 (d, J = 8.2 Hz, 2H), 6.82-6.80 (m, 3H), 6.77(s, 2H), 5.46 (s, 1H), 2.24 (s, 6H), 2.20 (s, 3H). 13 C NMR (101 MHz, CDCl3) δ145.6, 141.3, 140.28, 140.25, 140.2, 135.9, 135.4, 133.4, 132.4, 130.9,129.7, 129.4, 129.2, 129.1, 128.4, 128.2, 126.1, 26.4, 21.4.

[0044] HRMS (ESI): Accurate mass calculation C 29 H 26 Cl2Si [M+] + :472.1181, measured value 472.1193.

[0045] Embodiment 9: First, 2 mol% Pd2(dba)3·CH3Cl and 8 mol% ligand L9 were weighed into a Schlenk tube and replaced with N2 three times. 1 mL of cyclohexane was added and pre-stirred for 30 minutes. Then 45.2 mg of dihydrosilane and 66.6 mg of IIIi were added and stirred at 0°C for 6 hours. Then, the alkenylsilane product Ii was obtained by silica gel column chromatography (PE: EA = 50: 1), which was a yellow viscous oil (44.8 mg, 42% yield), 90% ee. HPLC conditions: using ultra-high performance liquid chromatography MD (Guangzhou Pheromon Scientific Instrument Co., Ltd.) column (n-hexane / isopropanol = 99.9:0.1, 0.5mL / min), λ = 254 nm, temperature = 20°C, the elution time of the minor enantiomer was 7.85 minutes, the elution time of the major enantiomer was 9.81 minutes, [α] D 20 = 12.4 (c = 0.78, CHCl3). 1 H NMR (400 MHz, CDCl3): δ 7.44 (d, J = 1.6 Hz, 1H), 7.42 (d, J = 1.6 Hz, 1H) 7.30-7.23 (m, 5H), 7.17-7.15 (m, H), 6.87 (d, J= 8.2 Hz, 2H), 6.79 (m, 3H), 6.74 (d, J =8.2 Hz, 2H), 5.45 (s, 1H), 2.25 (s, 6H), 2.21 (s, 3H). 1 3C NMR (101 MHz, CDCl3) δ 145.6, 141.3, 140.7, 140.4,140.3, 135.8, 133.3, 132.2, 131.3, 131.1, 129.8, 129.7, 129.1, 128.2, 126.0,121.7, 120.5, 77.5, 77.2, 76.8, 24.6, 21.4.

[0046] HRMS (ESI): Accurate mass calculation C 29 H 26 Br2Si [M+Na] + :495.1073, measured value 495.1061.

[0047] Embodiment 10: First, 2 mol% Pd2(dba)3·CH3Cl and 8 mol% ligand L1 were weighed into a Schlenk tube and replaced with N2 three times. 1 mL of toluene was added and pre-stirred for 30 minutes. Then 45.2 mg of dihydrosilane and 42.8 mg of IIIj were added and stirred at 0°C for 6 hours. Then, the alkenylsilane product Ij was obtained by silica gel column chromatography (PE: EA = 50: 1), which was a yellow viscous oil (79.2 mg, 90% yield), 90% ee. HPLC conditions: using ultra-high performance liquid chromatography MD (Guangzhou Pheromon Scientific Instrument Co., Ltd.) column (n-hexane / isopropanol = 99.9:0.1, 0.5mL / min), λ = 254 nm, temperature = 20°C, the elution time of the minor enantiomer was 7.67 min, the elution time of the major enantiomer was 9.86 min, [α] D 20 = 46.1 (c = 0.525, CHCl3). 1 H NMR (400 MHz, CDCl3): δ 7.44 (d, J = 1.6 Hz,1H), 7.42 (d, J = 1.6 Hz, 1H) 7.29-7.21 (m, 5H), 7.17-7.15 (m, H), 7.10-7.06(m, 1H) 7.00-6.95 (m, 1H) 6.83 (s, 1H), 6.79-6.65 (m, 7H), 6.56 (d, J =12.2Hz, 1H), 5.48 (s, 1H), 2.25 (s, 6H), 2.20 (s, 3H). 13 C NMR (101 MHz, CDCl3) δ164.4, 163.7, 162.0, 161.3, 145.7, 144.1, 144.0, 141.39, 141.37, 141.2,141.1, 140.3, 139.1, 139.0, 135.8, 133.3, 130.5, 130.4, 129.7, 129.6, 129.5,129.1, 128.2, 125.9, 125.5, 125.4, 123.8, 123.7, 116.2, 116.0, 115.2, 114.8,114.7, 114.5, 113.6, 113.4, 24.6, 21.4.

[0048] HRMS (ESI): Accurate mass calculation C 29 H 26Br2Si [M+Na] + :495.1073, measured value 495.1061.

[0049] Embodiment 11: First, 2 mol% Pd2(dba)3·CH3Cl and 8 mol% ligand L1 were weighed into a Schlenk tube and replaced with N2 three times. Tetrahydrofuran was added and pre-stirred for 30 minutes. Then 45.2 mg dihydrosilane and 42.8 mg IIIk were added and stirred at 0°C for 6 hours. Then, the alkenylsilane product Ik was obtained by silica gel column chromatography (PE: EA = 50: 1), which was a yellow viscous oil (86.2 mg, 98% yield), 91% ee. HPLC conditions: using ultra-high performance liquid chromatography MD (Guangzhou Pheromon Scientific Instrument Co., Ltd.) column (n-hexane / isopropanol = 99.9:0.1, 0.5mL / min), λ = 254 nm, temperature = 20°C, the elution time of the minor enantiomer was 10.07 minutes, the elution time of the major enantiomer was 13.53 minutes, [α] D 20 = 60.4 (c = 0.75, CHCl3) 1 H NMR (400 MHz, CDCl3): δ 7.47 (d, J = 1.6Hz,1H), 7.46 (d, J = 1.6Hz, 1H) 7.25-7.18 (m, 4H), 7.00-6.98 (m, 3H), 6.89-6.74(m, 6H), 6.68 (dd, J = 8.2Hz,1H), 5.54 (s, 1H), 2.28 (s, 6H), 2.19 (s, 3H). 13 C NMR (101 MHz, CDCl3) δ 161.7, 160.1, 159.3, 157.6, 145.8, 140.1, 137.2,137.2, 135.8, 133.6, 130.2, 130.2, 129.6, 129.5, 129.5, 129.4, 129.3, 129.1,128.9, 128.4, 128.3, 128.1, 126.2, 125.7, 125.5, 124.3, 124.3, 123.5, 123.5,116.0, 115.7, 115.5, 115.3, 24.6, 21.4.

[0050] HRMS (ESI): Accurate mass calculation C 29 H 26 Br2Si [M+Na] + :495.1073, measured value 495.1061.

[0051] Embodiment 12: First, 2 mol% Pd2(dba)3·CH3Cl and 8 mol% ligand L1 were weighed into a Schlenk tube and replaced with N2 three times. Cyclohexane was added and pre-stirred for 30 minutes. Then 42.4 mg dihydrosilane and 35.6 mg III l were added and stirred at 0°C for 6 hours. Then, the alkenylsilane product Il was obtained by silica gel column chromatography (PE: EA = 50: 1), which was a yellow viscous oil (69.4 mg, 89% yield), 85% ee. HPLC conditions: using an ultra-high performance liquid chromatography MD (Guangzhou Pheromon Scientific Instrument Co., Ltd.) column (n-hexane / isopropanol = 99.9:0.1, 0.5mL / min), λ = 254 nm, temperature = 20°C, the elution time of the minor enantiomer was 10.07 minutes, the elution time of the major enantiomer was 13.53 minutes, [α]D 25 = -7.63 (c = 0.80, CHCl3). 1 H NMR (400 MHz, CDCl3): δ 7.46 (d, J = 7.6Hz, 2H), 7.27-7.23 (m, 3H), 7.15-7.10 (m, 3H), 7.08-7.00 (m, 5H), 6.93-6.88(m, 3H), 5.52 (dd, J = 8.2 Hz,1H), 2.29 (s, 6H). 13 C NMR (101 MHz, CDCl3) δ145.7, 142.3, 142.1, 140.1, 137.3, 135.9, 133.9, 130.4, 130.2, 129.7, 129.5,128.8, 128.1, 128.1, 127.9, 127.9, 127.5, 126.4, 24.8. HRMS (APCI-TOF) m / z:[M + Na] + Calculate for C 28 H 26 Si, 413.1696, found 413.1693;

[0052] HRMS (ESI): Accurate mass calculation C 28 H 26 Si, [M+Na] + :413.1696, measured value 413.1693.

[0053] Embodiment 13: First, 2 mol% Pd2(dba)3·CH3Cl and 8 mol% ligand L1 were weighed into a Schlenk tube and replaced with N2 three times. Cyclohexane was added and pre-stirred for 30 minutes. Then 45.2 mg dihydrosilane and 57.2 mg IIIm were added and stirred at 0°C for 6 hours. Then, the alkenylsilane product Im was obtained by silica gel column chromatography (PE: EA = 50: 1), which was a yellow viscous oil (82.7 mg, 89% yield), 81% ee. HPLC conditions: using an ultra-high performance liquid chromatography MD (Guangzhou Pheromon Scientific Instrument Co., Ltd.) column (n-hexane / isopropanol = 99.9:0.1, 0.5 mL / min), λ = 254 nm, temperature = 20 °C, the elution time of the minor enantiomer was 7.79 min, the elution time of the major enantiomer was 8.71 min, [α] D25 = -7.63 (c = 0.80, CHCl3). 1 H NMR (400 MHz, CDCl3): δ 7.46 (d, J = 7.6 Hz,2H), 7.27-7.23 (m, 3H), 7.15-7.10 (m, 3H), 7.08-7.00 (m, 5H), 6.93-6.88 (m,3H), 5.52 (dd, J = 8.2 Hz,1H), 2.29 (s, 6H). 13 C NMR (101 MHz, CDCl3) δ 145.7,142.3, 142.1, 140.1, 137.3, 135.9, 133.9, 130.4, 130.2, 129.7, 129.5, 128.8,128.1, 128.1, 127.9, 127.9, 127.5, 126.4, 24.8. HRMS (APCI-TOF) m / z: [M + Na] + Calculate for C 28 H 26 Si, 413.1696, found 413.1693;

[0054] HRMS (ESI): Accurate mass calculation C 30 H 30 O2Si, [M+] + :450.2001, measured value 450.2002.

[0055] Embodiment 14: First, 2 mol% Pd2(dba)3·CH3Cl and 8 mol% ligand L1 were weighed into a Schlenk tube and replaced with N2 three times. 1 mL of cyclohexane was added and pre-stirred for 30 minutes. Then 45.2 mg of dihydrosilane and 38.0 mg of IIIn were added and stirred at 0°C for 6 hours. Then, the alkenylsilane product In was obtained by silica gel column chromatography (PE: EA = 10: 1), which was a yellow viscous oil (75.4 mg, 91% yield), 87% ee. HPLC conditions: using ultra-high performance liquid chromatography MD (Guangzhou Pheromon Scientific Instrument Co., Ltd.) column (n-hexane / isopropanol = 99.9:0.1, 0.5mL / min), λ = 254 nm, temperature = 20°C, the elution time of the minor enantiomer was 16.08 minutes, the elution time of the major enantiomer was 18.00 minutes, [α] D 20 = 35.6 (c = 1.0, CHCl3). 1 H NMR (400 MHz, CDCl3): δ 7.48 (d, J = 1.6 Hz, 1H), 7.46 (d, J = 1.6 Hz, 1H) 7.29-7.20 (m, 4H), 7.10 (s, 1H), 7.03 (d, J =6.0 Hz, 1H), 6.92-6.90 (m, 1H), 6.84 (d, J =5.2 Hz, 1H), 6.76 (m, 3H), 6.70 (d, J = 4.8 Hz, 1H) 5.45 (s, 1H), 2.25 (s, 6H), 2.20 (s, 3H). 13 C NMR (101MHz, CDCl3) δ 144.8, 141.0, 139.4, 139.1, 137.2, 134.8, 132.5, 129.5, 129.3,128.7, 127.9, 127.2, 127.2, 126.8, 125.2, 125.1, 125.1, 124.8, 23.6, 20.4.

[0056] HRMS (ESI): Accurate mass calculation C 25 H 24 S2Si, [M+Na] + :439.0981, measured value 439.0981.

[0057] Embodiment 15: First, 2 mol% Pd2(dba)3·CH3Cl and 8 mol% ligand L1 (12 mg) were weighed into a Schlenk tube and replaced with N2 three times. 1 mL of cyclohexane was added and pre-stirred for 30 minutes. Then 45.2 mg of dihydrosilane and 55.6 mg of Ⅲo were added and stirred at 0°C for 6 hours. Then, the alkenylsilane product Ⅰo was obtained by silica gel column chromatography (PE: EA = 20: 1), which was a yellow viscous oil (75.4 mg, 75% yield), 87% ee. HPLC conditions: using an ultra-high performance liquid chromatography MD (Guangzhou Pheromon Scientific Instrument Co., Ltd.) column (n-hexane / isopropanol = 99.9:0.1, 0.5 mL / min), λ = 254 nm, temperature = 20 °C, the elution time of the minor enantiomer was 16.08 min, the elution time of the major enantiomer was 18.00 min, [α] D 20 = 42.3 (c = 0.74, CHCl3). 1 H NMR (400 MHz, CDCl3): δ 7.63-7.47(m, 8H), 7.44-7.42(m, 2H) 7.28 - 7.14 (m, 9H) 7.12 - 7.10 (m, 1H) 6.93-6.90(m, 1H) 7.45 (d, J = 6.0Hz, 2H), 5.61 (s, 1H), 2.28 (s, 6H), 2.17 (s, 3H). 13 CNMR (101 MHz, CDCl3) δ 145.7, 142.6, 140.4, 140.1, 139.9, 136.0, 135.1,134.1, 133.9, 133.3, 132.7, 132.2, 129.6, 129.5, 129.0, 128.3, 128.2, 128.1,128.1, 127.8, 127.6, 127.4, 127.3, 127.1, 126.8, 126.6, 126.2, 126.1, 125.9,125.6, 24.7, 21.4.

[0058] HRMS (ESI): Accurate mass calculation C 25 H 24 S2Si, [M+K] + :543.1905, measured value 543.1919.

[0059] Embodiment 16: First, 2 mol% Pd2(dba)3·CH3Cl and 8 mol% ligand L1 (12 mg) were weighed into a Schlenk tube and replaced with N2 three times. 1 mL of toluene was added and pre-stirred for 30 minutes. Then 45.2 mg of dihydrosilane and 36.0 mg of IIIp were added and stirred at 0°C for 6 hours. Then, the alkenylsilane product Ip was obtained by silica gel column chromatography (PE: EA = 2: 1), which was a yellow viscous oil (30.4 mg, 38% yield), 87% ee. HPLC conditions: using ultra-high performance liquid chromatography MD (Guangzhou Pheromon Scientific Instrument Co., Ltd.) column (n-hexane / isopropanol = 99.9:0.1, 0.5mL / min), λ = 254 nm, temperature = 20°C, the elution time of the minor enantiomer is 5.20 minutes, the elution time of the major enantiomer is 6.06 minutes, [α] D 25 = 21.5 (c = 0.2, CHCl3). 1 H NMR (400 MHz, CDCl3): δ 8.35 (dd, J = 1.6Hz, 1H), 8.28 (dd, J = 1.6 Hz, 1H), 8.24 (d, J = 2.8 Hz, 1H), 8.19 (d, J =1.6Hz, 1H), 7.49 (d, J = 1.6 Hz, 1H), 7.47 (d, J = 1.6 Hz, 1H), 7.34 - 7.27(m, 4H), 7.20 (s, 1H), 7.10 - 7.07 (m, 2H), 6.97 - 6.93 (m, 2H), 6.80 (s,2H), 5.52 (s, 1H), 2.27 (s, 6H), 2.22 (s, 3H). 13C NMR (101 MHz, CDCl3) δ150.7, 148.6, 148.5, 147.8, 145.6, 140.6, 140.3, 140.2, 136.1, 135.9, 135.7,132.5, 130.0, 129.2, 128.4, 125.2, 123.8, 123.1, 24.6, 21.4.

[0060] HRMS (ESI): Accurate mass calculation C 27 H 26 N2Si, [M+Na] + :429.1757, measured value 429.1755.

[0061] Embodiment 17: First, 2 mol% Pd2(dba)3·CH3Cl and 8 mol% ligand L1 (12 mg) were weighed into a Schlenk tube and replaced with N2 three times. 1 mL of tetrahydrofuran was added and pre-stirred for 30 minutes. Then 45.2 mg of dihydrosilane and 30.2 mg of IIIq were added and stirred at 0°C for 6 h. Then, the alkenylsilane product Iq was purified by silica gel column chromatography (PE: EA = 50: 1), and 2r was obtained by silica gel column chromatography ((petroleum ether: ethyl acetate = 5: 1)) as a yellow viscous oil (49.4 mg, 66% yield), 75% ee. HPLC conditions: using ultra-high performance liquid chromatography MD (Guangzhou Pheromon Scientific Instrument Co., Ltd.) column (n-hexane / isopropanol = 95: 5, 0.5 mL / min), λ = 254 nm, temperature = 20 °C, the elution time of the minor enantiomer was 4.54 minutes, the elution time of the major enantiomer was 4.89 minutes, [α] D 20 = -57.6 (c = 0.85, CHCl3). 1H NMR (400 MHz, CDCl3): δ 7.54 (d, J = 1.6 Hz, 1H), 7.52 (d, J = 1.6Hz, 1H), 7.31 - 7.23 (m, 3H), 6.76 (s, 2H), 5.42 (s, 1H), 5.19 (d, J = 10 Hz,1H), 4.17 (t, J = 16.4 Hz, 2H), 3.62 (m, 2H), 2.27 (s, 6H), 2.19 (s, 3H),1.66 (dq, J = 35.2Hz, 3H), 0.87 (m, 2H), 0.41(m, 2H). 13 C NMR (101 MHz, CDCl3)δ 156.3, 150.6, 145.6, 140.3, 135.8, 133.2, 130.4, 129.7, 129.0, 128.2,125.8, 62.2, 46.8, 24.5, 21.3, 12.0, 7.84, 7.79.

[0062] HRMS (ESI): Accurate mass calculation C 27 H 26 N2Si, [M+Na] + :416.1477 , measured value 416.1477.

[0063] Embodiment 18: First, 2 mol% Pd2(dba)3·CH3Cl and 8 mol% ligand L1 (12 mg) were weighed into a Schlenk tube and replaced with N2 three times. 1 mL of cyclohexane was added and pre-stirred for 30 minutes. Then 45.2 mg of dihydrosilane and 41.8 mg of IIIr were added and stirred at 0°C for 6 h. Then, the alkenylsilane product Ir was obtained by silica gel column chromatography (PE: EA = 50: 1), and 2s was obtained by silica gel column chromatography (petroleum ether: ethyl acetate = 5: 1), which was a yellow viscous oil (40.4 mg, yield 46%), 92% ee. HPLC conditions: using an ultra-high performance liquid chromatography MD (Guangzhou Pheromon Scientific Instrument Co., Ltd.) column (n-hexane / isopropanol = 95: 5, 0.5 mL / min), λ = 254 nm, temperature = 20 °C, the elution time of the minor enantiomer was 9.84 minutes, the elution time of the major enantiomer was 11.14 minutes, [α] D 20= 9.9 (c = 3.0, CHCl3). 1 H NMR (400 MHz, CDCl3): δ 7.60 (d, J = 1.6 Hz, 1H), 7.58 (d, J = 1.6 Hz, 1H), 7.48 - 7.46(m, 2H), 7.36 - 7.21 (m, 6H), 6.82 (s, 2H), 6.73 (s, 1H), 5.57 (s,1H), 2.89 (s, 3H), 2.48 (s, 3H), 2.38 (s, 6H), 2.22 (s, 3H). 13 C NMR (101MHz, CDCl3) δ 145.5, 140.1, 139.5, 135.6, 135.4, 133.7, 129.6, 129.0, 128.8,128.4, 128.1, 126.6, 126.1, 119.9, 77.5, 77.2, 76.8, 37.6, 35.9, 24.5, 21.3.

[0064] HRMS (ESI): Accurate mass calculation C 27 H 26 N2Si, [M+Na] + :416.1477 , measured value 416.1477.

[0065] Embodiment 19: First, 2 mol% Pd2(dba)3·CH3Cl and 8 mol% ligand L1 (12 mg) were weighed into a Schlenk tube and replaced with N2 three times. 1 mL of cyclohexane was added and pre-stirred for 30 minutes. Then 45.2 mg of dihydrosilane and 41.6 mg of Is were added and stirred at 0°C for 6 hours. Then, the alkenylsilane product Ⅰs was obtained by silica gel column chromatography (PE: EA = 5: 1), which was a yellow viscous oil (72.7 mg, 84% yield), 87% ee. HPLC conditions: using ultra-high performance liquid chromatography MD (Guangzhou Pheromon Scientific Instrument Co., Ltd.) column (n-hexane / isopropanol = 95: 5, 0.5 mL / min), λ = 254 nm, temperature = 20 °C, the elution time of the minor enantiomer is 8.61 minutes, the elution time of the major enantiomer is 10.85 minutes, [α] D 20 = 10.8 (c = 3.0, CHCl3). 1H NMR (400 MHz, CDCl3): δ 7.56 (d, J =1.6Hz, 1H), 7.54 (d, J = 1.6Hz, 1H), 7.24-7.22 (m, 5H), 7.17 (dd, J = 14.7Hz,3H), 7.08 (dd, J = 16.1 Hz, 2H), 6.94(s, 1H), 6.78-6.73 (m, 3H), 6.56 - 6.54(d, J = 8.7 Hz, 2H), 5.55 (s, 1H), 4.92 (q, J = 33.3, 11.8 Hz, 2H), 2.30 (s,6H), 2.18 (s, 3H). 13 C NMR (101 MHz, CDCl3): δ 158.6, 145.4, 144.2, 139.7,137.4, 136.7, 136.0, 134.3, 129.4, 129.3, 128.9, 128.9, 128.5, 128.5, 128.1,127.8, 127.5, 120.8, 114.8, 68.4, 24.5, 21.3

[0066] HRMS (ESI): Accurate mass calculation C 30 H 30 OSi, [M+Na] + :457.1958, measured value 457.1952.

[0067] Embodiment 20: First, 2 mol% Pd2(dba)3·CH3Cl and 8 mol% ligand L1 (12 mg) were weighed into a Schlenk tube and replaced with N2 three times. 1 mL of cyclohexane was added and pre-stirred for 30 minutes. Then 45.2 mg of dihydrosilane and 51.6 mg of IIIt were added and stirred at 0°C for 6 hours. Then, the alkenylsilane product It was obtained by silica gel column chromatography (PE: EA = 2: 1), which was a yellow viscous oil (87.9 mg, 91% yield), 84% ee. HPLC conditions: using an ultra-high performance liquid chromatography MD (Guangzhou Pheromon Scientific Instrument Co., Ltd.) column (n-hexane / isopropanol = 95: 5, 0.5 mL / min), λ = 254 nm, temperature = 20 °C, the elution time of the minor enantiomer was 9.86 minutes, the elution time of the major enantiomer was 10.95 minutes, [α] D 20= -42.0 (c = 0.1, CHCl3). 1 H NMR (400 MHz, CDCl3): δ 7.70-7.65(m, 3H),7.60-7.58(m, 3H) 7.36 - 7.33(m, 2H), 7.28-7.24(m, 4H), 7.10-7.04 (m, 3H),6.79-6.75(m, 3H), 6.57(d, J = 7.6Hz, 2H), 5.55(s, 1H), 4.95(q, J = 11.6Hz,2H), 2.33(s, 6H), 2.19(s, 3H). 13 C NMR (101 MHz, CDCl3): δ 158.6, 145.4,144.4, 139.7, 137.1, 136.1, 134.8, 134.3, 133.2, 132.7, 129.5, 129.4, 128.9,128.3, 128.2, 128.1, 128.0, 127.7, 127.4, 126.8, 126.5, 120.8, 114.8, 68.4,24.6, 21.4

[0068] HRMS (ESI): Accurate mass calculation C 34 H 32 OSi, [M+Na] + :507.2115 , measured value 507.2115.

[0069] Application Example 1 The preparation method provided by the present invention can introduce silicon chirality into the alkynyl drug fragment (as shown in the following reaction formula A), thereby realizing the chiral construction of silicon-containing drugs; or introduce silicon chirality into the alkynyl polymer (as shown in the following reaction formula B), prepare silicon-containing chiral polymers, and apply them in optoelectronic materials.

[0070] The examples in the above specific implementation scheme are illustrative rather than restrictive, and several examples can be cited according to the limited scope. Therefore, any changes and modifications made without departing from the overall concept of the present invention should fall within the scope of protection defined by the present invention.

Claims

1. A silicon-containing chiral alkenyl silicon hydride compound, characterized in that: The chemical structural formula of the silicon-containing chiral alkenyl silicon hydride compound is shown in the following formula (I): In formula (I), * represents chirality, which is R or S; Among them, R 1 for or ; R 2 , R 3 Independently selected from one of the following structures: Phenyl, , , , , , , , , , , , , , , , , , , .

2. The silicon-containing chiral alkenyl silicon hydride compound according to claim 1, characterized in that: The chemical structural formula of the silicon-containing chiral alkenyl silicon hydride compound is selected from any one of the following Ia to It: 。 3. A method for preparing a silicon-containing chiral alkenyl silicon hydride compound according to any one of claims 1 to 2, characterized in that: The preparation method comprises the following steps: In the presence of a phosphine ligand, a palladium catalyst and a reaction medium, a dihydrosilane represented by formula (II) and an alkynyl compound represented by formula (III) are subjected to an asymmetric hydrosilylation reaction to synthesize a silicon-containing chiral alkenyl silicon hydride compound represented by formula (I); the reaction formula is shown below: Among them, R 1 for or ; R 2 , R 3 Independently selected from one of the following structures: Phenyl, , , , , , , , , , , , , , , , , , , .

4. The preparation method according to claim 3, characterized in that: The palladium catalyst is selected from Pd2(dba)3·CH3Cl, Pd2(dba) 3、 One of Pd(OAc)2, Pd(cod)2Cl2, Pd(nbd)2Cl2, and Pd(acac)2.

5. The preparation method according to claim 3, characterized in that: The phosphine ligand is selected from one or more of the following compounds L1 to L9: 。 6. The preparation method according to claim 3, characterized in that: The method specifically comprises: in an inert gas atmosphere, pre-stirring the phosphine ligand, the palladium catalyst and the reaction medium for 30 to 45 minutes, then sequentially adding the dihydrosilane represented by formula (II) and the alkynyl compound represented by formula (III), and reacting them at 0 to 40° C. for 2 to 18 hours to obtain a silicon-containing chiral alkenyl silicon hydride compound.

7. The preparation method according to claim 6, characterized in that: The molar ratio of the dihydrosilane represented by formula (II), the alkynyl compound represented by formula (III), the palladium catalyst, and the phosphine ligand is 1:1:(0.001-0.003):(0.06-0.10).

8. The preparation method according to claim 6, characterized in that: The reaction medium is any one of toluene, tetrahydrofuran, dichloromethane, n-hexane and cyclohexane.

9. The preparation method according to claim 6, characterized in that: After the reaction is completed, a post-treatment step is also included; the post-treatment includes: removing the solvent by rotary evaporation, and separating and purifying the crude product by silica gel column chromatography.

10. Use of the silicon-containing chiral alkenyl silicon hydride compound according to any one of claims 1 to 2 in the preparation of molecular probes or organic optoelectronic functional materials.

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