Preparation method of arylsilane compound containing norbornene

Abstract

The invention discloses a preparation method of an aryl silane compound containing norbornene. According to the method, hexamethyldisilane is used as a silicon source, a five-membered palladium ring transition state is formed through catalysis of a palladium catalyst under the mediation effect of norbornene, ortho-position C-H functionalization of aryl thianthrene onium salt is further achieved, and aryl silane containing norbornene is obtained. Aryl silane has important practical significance, can improve the performance of macromolecules and optical materials in the field of materials, also has outstanding effects in the aspects of electronics, electricity and surface treatment, is also applied to the fields of biological medicine and energy, provides powerful support for multi-industry development, and has wide application prospects. The arylsilane compound containing norbornene is synthesized in one step through a one-pot method, and a new path and method are provided for preparing the novel arylsilane compound.

Description

Technical Field

[0001] The invention belongs to the technical field of organic synthesis, and in particular relates to a method for synthesizing an aryl silane compound containing norbornene. Background Art

[0002] Organosilicon compounds have unique chemical properties and biological activities. In addition to being widely used in organic chemistry, they are also widely used in materials science. 1 , Medicine and Biology 2 , electronic and optical materials 3 Therefore, the synthesis research of organosilane compounds has attracted the attention of more and more scientists.

[0003] Silicon-based compounds play a variety of roles in drug molecules. They can construct complex carbon skeletons, introduce stereochemical elements, and help synthesize active drug molecules. They also affect pharmacokinetic properties, optimize absorption, regulate distribution, change metabolic rate, improve drug efficacy and reduce side effects. Many drugs containing silicon groups have been widely used in drug development, such as Amsilarotene. 4 , Zirosilone 5 , Loratadine 6 , Doxylamine 7 wait.

[0004] At present, the preparation methods of organosilane compounds mainly include the following: ① Direct synthesis method: Organosilane compounds are prepared by direct reaction of silicon with halogenated hydrocarbons or alkoxy hydrocarbons. This method usually needs to be carried out under high temperature and high pressure, and the reaction conditions are relatively harsh. ② Grignard reagent method: Use Grignard reagent to react with halogenated silane to generate organosilane compounds. This method has mild reaction conditions and high yield, but it requires the use of flammable and explosive Grignard reagents, which is dangerous to operate. ③ Hydrosilation reaction method: In the presence of a catalyst, organosilane compounds are prepared by the addition reaction of unsaturated compounds with hydrosilane. ④ Silylation reaction method: Through the reaction of silane with other compounds, silane groups are introduced into other molecules to prepare organosilane compounds. In recent years, hexamethyldisilane has received increasing attention due to its atomic and step economy. Compared with other silicon reagents, hexamethyldisilane has the advantages of stable properties, low toxicity and insensitivity to air. In recent years, a large number of literatures have reported on the synthesis strategies of palladium-catalyzed synthesis of silicon-substituted compounds, as listed below:

[0005] Hiyama 8The research group reported a palladium-catalyzed, ligand-controlled silylation reaction of aryl halides with hexamethyldisilane.

[0006] Nakadaira Yasuhiro 9 The research team discovered that under palladium catalysis, organodisilane reacts with butadiene or isoprene in a 1:2 addition reaction. However, the reaction rate is relatively slow and the yield of the target product is low.

[0007] Naoto Chatani 10 The research group reported the Rh-catalyzed silylation of aryl cyanides with hexamethyldisilane. The strong carbon-cyanide (C-CN) bond can be broken without the aid of a small ring or special coordination groups, providing a new method for the construction of C-Si bonds.

[0008] Zhang 11 The research group has developed a palladium-catalyzed method for the efficient synthesis of disilylation products from aryl halides. The reaction substrate range is wide, and various aromatic halides can be disilylated through three types of CH activation, including C(sp 2 )-H、C(sp 3 )-H and remote CH bond activation.

[0009] John Spence 12 The research group synthesized the first palladium complex of nitrogen-containing heterocyclic carbene [(NHC)2Pd(SiMe3)2] at room temperature, which was produced by the oxidative addition reaction of hexamethyldisilane to palladium species. The [(NHC)2Pd(SiMe3)2] complex was used as a catalyst for the disilylation reaction of non-activated disilanes with alkynes. A series of 1,2-disilyl diphenylethylenes were synthesized with high yield and 100% cis stereoselectivity.

[0010] In summary, (1) compared with hydrogen silane reagents, hexamethyldisilane has the advantages of low price, insensitivity to air and water, relatively stable properties, and easy storage, and is a good silicon source. (2) Aryl silanes are of great significance in the fields of organic synthesis, electronic devices, and drug synthesis. For example, in the field of drug synthesis, aryl silanes can optimize the molecular structure and activity by changing the spatial configuration and electron distribution of drug molecules, enhance the ability of drugs to bind to targets, and improve biological activity; at the same time, they can adjust properties such as lipophilicity and water solubility to improve pharmacokinetics and help drugs to better exert their effects in the body. In addition, they can also be modified and combined with targeting groups to achieve targeted drug delivery, reduce side effects, and improve the safety and effectiveness of drug treatment. Therefore, the development of novel and efficient methods for constructing aryl silane compounds is of great significance. Summary of the invention

[0011] The technical problem to be solved by the present invention is to use hexamethyldisilane, which is stable, low in toxicity and insensitive to air, as a silicon source, and to form a five-membered palladium ring transition state through a palladium catalyst under the mediation of norbornene, thereby realizing the ortho-CH functionalization of an arylthianthrinium salt and obtaining an aryl silane containing norbornene.

[0012] In order to solve the above technical problems, the technical solution adopted by the present invention is: aryl thianthrenium salt, norbornene and hexamethyldisilane are used as substrates to prepare aryl silane compounds containing norbornene. It includes the following steps: adding a compound having the general formula I, compound A, compound B, a catalyst, and a solvent into a pressure-resistant tube, filling with argon gas, reacting at 110-120°C for 5 hours, and monitoring the reaction process by thin layer chromatography until the reaction is complete. Extract with ethyl acetate and saturated brine, dry with anhydrous sodium sulfate, evaporate the solvent under reduced pressure, and separate and purify the residue by silica gel column chromatography using petroleum ether / ethyl acetate as the mobile phase to obtain compound II. The reaction equation is as follows: In the formula: R is a hydrogen atom, a methyl group, an ethyl group, a tert-butyl group, a phenyl group, a chlorine group, a fluorine group, a methoxy group, or an N,N-dimethyl group.

[0013] The method for preparing the norbornene-containing arylsilane compound is characterized in that the molar ratio of compound I to compound A, compound B and catalyst is 1:2.0-3.0:2.0-3.0:0.1.

[0014] The method for preparing the norbornene-containing arylsilane compound is characterized in that the catalyst is palladium acetate, bis(triphenylphosphine)palladium dichloride, or tetrakis(triphenylphosphine)palladium.

[0015] The method for preparing the norbornene-containing arylsilane compound is characterized in that the ligand is triphenylphosphine, bis(diphenylphosphino)methane, or 1,4-bis(diphenylphosphino)butane.

[0016] The method for preparing the norbornene-containing arylsilane compound is characterized in that the solvent is acetonitrile, tetrahydrofuran, toluene, or N,N-dimethylformamide.

[0017] The method for preparing the norbornene-containing arylsilane compound is characterized in that the reaction temperature is 110-120°C.

[0018] Compared with the prior art, the present invention has the following advantages: the present invention innovatively proposes a method for preparing an aryl silane compound containing norbornene using aryl thianthrenium salt, norbornene and hexamethyldisilane as substrates, the substrate used is cheap and easily available, the operation is simple, the substrate compatibility is good, the yield is high, and the method has the potential for industrial production. DETAILED DESCRIPTION

[0019] The technical solution of the present invention is further described in detail below through embodiments. The specific implementation is as follows:

[0020] Embodiment 1: The preparation method of this embodiment comprises the following steps:

[0021] Palladium acetate (0.5mmol, 112mg), triphenylphosphine (0.5mmol, 131mg), acetonitrile (5mL), compound Ia (5mmol, 1.16g), compound A (10mmol, 1.46g), and compound B (10mmol, 0.94g) were added to a 20mL pressure tube in sequence, and argon was filled in. The mixture was reacted at 120°C for 5.0h, and the reaction progress was monitored by thin layer chromatography until the reaction was complete; the mixture was extracted with ethyl acetate and saturated brine, dried with anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The residue was separated and purified by silica gel column chromatography using petroleum ether / ethyl acetate (200:1) as the mobile phase to obtain compound IIa with a yield of 88%. The reaction equation is as follows:

[0022] Embodiment 2: The preparation method of this embodiment comprises the following steps:

[0023] Palladium acetate (0.5mmol, 112mg), triphenylphosphine (0.5mmol, 131mg), acetonitrile (5mL), compound Ib (5mmol, 1.23g), compound A (10mmol, 1.46g), and compound B (10mmol, 0.94g) were added to a 20mL pressure tube in sequence, and argon was filled in. The mixture was reacted at 120°C for 5.0h, and the reaction progress was monitored by thin layer chromatography until the reaction was complete. The mixture was extracted with ethyl acetate and saturated brine, dried with anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The residue was separated and purified by silica gel column chromatography using petroleum ether / ethyl acetate (200:1) as the mobile phase to obtain compound IIb with a yield of 91%. The reaction equation is as follows:

[0024] Embodiment 3: The preparation method of this embodiment comprises the following steps:

[0025] Palladium acetate (0.5mmol, 112mg), triphenylphosphine (0.5mmol, 131mg), acetonitrile (5mL), compound Ic (5mmol, 1.30g), compound A (10mmol, 1.46g), and compound B (10mmol, 0.94g) were added to a 20mL pressure tube in sequence, and argon was filled in. The mixture was reacted at 120°C for 5.0h, and the reaction progress was monitored by thin layer chromatography until the reaction was complete; the mixture was extracted with ethyl acetate and saturated brine, dried with anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The residue was separated and purified by silica gel column chromatography using petroleum ether / ethyl acetate (200:1) as the mobile phase to obtain compound IIc with a yield of 80%. The reaction equation is as follows:

[0026] Embodiment 4: The preparation method of this embodiment comprises the following steps:

[0027] Palladium acetate (0.5mmol, 112mg), triphenylphosphine (0.5mmol, 131mg), acetonitrile (5mL), compound Id (5mmol, 1.44g), compound A (10mmol, 1.46g), and compound B (10mmol, 0.94g) were added to a 20mL pressure tube in sequence, and argon was filled in. The mixture was reacted at 120°C for 5.0h, and the reaction progress was monitored by thin layer chromatography until the reaction was complete. The mixture was extracted with ethyl acetate and saturated brine, dried with anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The residue was separated and purified by silica gel column chromatography using petroleum ether / ethyl acetate (200:1) as the mobile phase to obtain compound IId with a yield of 80%. The reaction equation is as follows:

[0028] Embodiment 5: The preparation method of this embodiment comprises the following steps:

[0029] Palladium acetate (0.5mmol, 112mg), triphenylphosphine (0.5mmol, 131mg), acetonitrile (5mL), compound Ie (5mmol, 1.54g), compound A (10mmol, 1.46g), and compound B (10mmol, 0.94g) were added to a 20mL pressure tube in sequence, and argon was filled in. The mixture was reacted at 120°C for 5.0h, and the reaction progress was monitored by thin layer chromatography until the reaction was complete; the mixture was extracted with ethyl acetate and saturated brine, dried with anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The residue was separated and purified by silica gel column chromatography using petroleum ether / ethyl acetate (200:1) as the mobile phase to obtain compound IIe with a yield of 85%. The reaction equation is as follows:

[0030] Embodiment 6: The preparation method of this embodiment comprises the following steps:

[0031] Palladium acetate (0.5mmol, 112mg), triphenylphosphine (0.5mmol, 131mg), acetonitrile (5mL), compound If (5mmol, 1.25g), compound A (10mmol, 1.46g), and compound B (10mmol, 0.94g) were added to a 20mL pressure tube in sequence, and argon was filled in. The mixture was reacted at 120°C for 5.0h, and the reaction progress was monitored by thin layer chromatography until the reaction was complete. The mixture was extracted with ethyl acetate and saturated brine, dried with anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The residue was separated and purified by silica gel column chromatography using petroleum ether / ethyl acetate (200:1) as the mobile phase to obtain compound IIf with a yield of 77%. The reaction equation is as follows:

[0032] Embodiment 7: The preparation method of this embodiment comprises the following steps:

[0033] Palladium acetate (0.5mmol, 112mg), triphenylphosphine (0.5mmol, 131mg), acetonitrile (5mL), compound Ig (5mmol, 1.33g), compound A (10mmol, 1.46g), and compound B (10mmol, 0.94g) were added to a 20mL pressure tube in sequence, and argon was filled in. The mixture was reacted at 120°C for 5.0h, and the reaction process was monitored by thin layer chromatography until the reaction was complete; the mixture was extracted with ethyl acetate and saturated brine, dried with anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The residue was separated and purified by silica gel column chromatography using petroleum ether / ethyl acetate (200:1) as the mobile phase to obtain compound IIg with a yield of 76%. The reaction equation is as follows:

[0034] Embodiment 8: The preparation method of this embodiment comprises the following steps:

[0035] Palladium acetate (0.5mmol, 112mg), triphenylphosphine (0.5mmol, 131mg), acetonitrile (5mL), compound Ih (5mmol, 1.31g), compound A (10mmol, 1.46g), and compound B (10mmol, 0.94g) were added to a 20mL pressure tube in sequence, and argon was filled in. The mixture was reacted at 120°C for 5.0h, and the reaction progress was monitored by thin layer chromatography until the reaction was complete; the mixture was extracted with ethyl acetate and saturated brine, dried with anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The residue was separated and purified by silica gel column chromatography using petroleum ether / ethyl acetate (100:1) as the mobile phase to obtain compound IIh with a yield of 86%. The reaction equation is as follows:

[0036] Embodiment 9: The preparation method of this embodiment comprises the following steps:

[0037] Palladium acetate (0.5mmol, 112mg), triphenylphosphine (0.5mmol, 131mg), acetonitrile (5mL), compound Ii (5mmol, 1.38g), compound A (10mmol, 1.46g), and compound B (10mmol, 0.94g) were added to a 20mL pressure tube in sequence, and argon was filled in. The mixture was reacted at 120°C for 5.0h, and the reaction progress was monitored by thin layer chromatography until the reaction was complete; the mixture was extracted with ethyl acetate and saturated brine, dried with anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The residue was separated and purified by silica gel column chromatography using petroleum ether / ethyl acetate (200:1) as the mobile phase to obtain compound IIi with a yield of 72%. The reaction equation is as follows:

[0038] Embodiment 10: The preparation method of this embodiment comprises the following steps:

[0039] Palladium acetate (0.5mmol, 112mg), triphenylphosphine (0.5mmol, 131mg), acetonitrile (5mL), compound Ij (5mmol, 1.23g), compound A (10mmol, 1.46g), and compound B (10mmol, 0.94g) were added to a 20mL pressure tube in sequence, and argon was filled in. The mixture was reacted at 120°C for 5.0h, and the reaction progress was monitored by thin layer chromatography until the reaction was complete; the mixture was extracted with ethyl acetate and saturated brine, dried with anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The residue was separated and purified by silica gel column chromatography using petroleum ether / ethyl acetate (200:1) as the mobile phase to obtain compound IIj with a yield of 76%. The reaction equation is as follows:

[0040] Embodiment 11: The preparation method of this embodiment comprises the following steps:

[0041] Palladium acetate (0.5mmol, 112mg), triphenylphosphine (0.5mmol, 131mg), acetonitrile (5mL), compound Ik (5mmol, 1.23g), compound A (10mmol, 1.46g), and compound B (10mmol, 0.94g) were added to a 20mL pressure tube in sequence, and argon was filled in. The mixture was reacted at 120°C for 5.0h, and the reaction progress was monitored by thin layer chromatography until the reaction was complete. The mixture was extracted with ethyl acetate and saturated brine, dried with anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The residue was separated and purified by silica gel column chromatography using petroleum ether / ethyl acetate (200:1) as the mobile phase to obtain compound IIk with a yield of 78%. The reaction equation is as follows:

[0042] The structure, NMR and high-resolution mass spectrometry data of the product obtained in Example 1 are as follows:

[0043] 1 H NMR (400MHz, CDCl3, ppm): δ = 7.39 (d, J = 7.6Hz, 2H), 7.27-7.31 (m, 1H), 7.11-7.15 (m, 1H), 3.15 (d, J = 10.4Hz, 1H), 2.32-2.36 (m, 1H), 1.96 -1.99(m,1H),1.73-1.78(m,1H),1.57-1.62(m,1H),1.42-1.45(m,1H),1.35-1.38(m,2H),1.25-1.28(m,1H),0.32(s,9H),-0.37(s,9H); 13 HRMS calcd for C 19 H 33 Si2[M+H] + 317.2116; found:317.2112.

[0044] The structure, NMR and high-resolution mass spectrometry data of the product obtained in Example 2 are as follows:

[0045] 1 H NMR (400MHz, CDCl3, ppm): δ = 7.28 (d, J = 8.0Hz, 1H), 7.18 (s, 1H), 7.95 (d, J = 6.0Hz, 1H), 3.12 (d, J = 10.4Hz, 1H), 1.96 (d, J = 9.6Hz ,1H),1.71-1.75(m,1H),1.55-1.61(m,1H),1.38-1.43(m,1H),1.32-1.36(m,2H),1.23-1.26(m,2H),0.31(s,9H),-0.36(s,9H); 13 HRMS calcd for C 20 H 35 Si2[M+H] + 331.2272; found:331.2264.

[0046] The structure, NMR and high-resolution mass spectrometry data of the product obtained in Example 3 are as follows:

[0047] 1 H NMR (400MHz, CDCl3, ppm): δ = 7.30 (d, J = 8.0Hz, 1H), 7.21 (s, 1H), 7.12 (d, J = 6. 8Hz,1H),3.13(d,J=10.4Hz,1H),2.56-2.62(m,2H),2.30-2.35(m,2H),1.97( d,J=9.2Hz,1H),1.71-1.75(m,1H),1.55-1.61(m,1H),1.38-1.44(m,1H),1.3 4(d,J=9.6Hz,2H),1.26(s,1H),1.19-1.23(m,3H),0.32(s,9H),-0.37(s,9H); 13 HRMS calcd for C 21 H 37Si2[M+H]+345.2429; found:345.2412.

[0048] The structure, NMR and high-resolution mass spectrometry data of the product obtained in Example 4 are as follows:

[0049] 1 H NMR (400MHz, CDCl3, ppm): δ = 7.42 (s, 1H), 7.30-7.31 (m, 2H), 3.13 (d, J = 10.0Hz, 1H), 2.34 (s, 2H), 1.97 (d, J = 9.6Hz, 1H), 1.72-1.75 ( m,1H),1.55-1.61(m,1H),1.41-1.42(m,1H),1.35(d,J=9.2Hz,2H),1.30(s,9H),1.24(d,J=10.4Hz,1H),0.33(s,1H),-0.39(s,1H); 13 CNMR (100MHz, CDCl3, ppm): δ=149.7,147.4,138.1,130.9,126.2,126.1,50.6,44.8,43.6,38.9,38.6,34.4,32.8,32.2,31.5,1.1,-0.8.HRMS calcd forC 23 H 41 Si2[M+H] + 373.2742; found:373.2726.

[0050] The structure, NMR and high-resolution mass spectrometry data of the product obtained in Example 5 are as follows:

[0051] 1 H NMR (400MHz, CDCl3, ppm): δ = 7.63 (d, J = 2.0Hz, 1H), 7.59 (s, 1H), 7.57 (s, 1H), 7.52-7.5 5(m,1H),7.47(d,J=8.0Hz,1H),7.39-7.43(m,2H),7.28-7.32(m,1H),7.20(d,J=10.4Hz ,1H),2.37(t,J=10.0Hz,2H),2.00(d,J=10.4Hz,1H),1.73-1.80(m,1H),1.59-1.65(m,1 H),1.44-1.47(m,1H),1.35-1.41(m,2H),1.28-1.31(m,1H),0.37(s,9H),-0.34(s,9H);13 C NMR (100MHz, CDCl3, ppm): δ=152.0,141.5,139.5,137.7,132.9,128.7,127.9, 127.1,127.0,126.9,50.9,45.0,43.6,38.9,38.6,32.8,32.2,1.0,-0.7.HRMS calcd forC 25 H 37 Si2[M+H] + 393.2429; found:393.2433.

[0052] The structure, NMR and high-resolution mass spectrometry data of the product obtained in Example 6 are as follows:

[0053] 1 H NMR (400MHz, CDCl3, ppm): δ=7.33-7.36(m,1H),7.06-7.09(m,1H),6.93-6.98(m,1H),3.13(d,J=10.4Hz,1H),2.35(d,J=2.8Hz,1H),2.27(d,J=2.4H z,1H),1.91-1.94(m,1H),1.72-1.76(m,1H),1.57-1.62(m,1H),1.40-1.4 3(m,1H),1.34-1.37(m,2H),1.24-1.27(m,1H),0.32(s,9H),-0.35(s,9H); 13 HRMScalcd for C 19 H 32 FSi2[M+H] + 335.2021; found:335.2018.

[0054] The structure, NMR and high-resolution mass spectrometry data of the product obtained in Example 7 are as follows:

[0055] 1H NMR (400MHz, CDCl3, ppm): δ = 7.31-7.33 (m, 2H), 7.23-7.26 (m, 1H), 3.11 (d, J = 10.4Hz, 1H), 2.35 (d, J = 3.6Hz, 1H), 2.26 (d, J = 2.4Hz, 1H), 1.91 (d,J=10.0Hz,1H),1.72-1.76(m,1H),1.56-1.62(m,1H),1.40-1.43(m ,1H),1.34-1.37(m,2H),1.23-1.27(m,1H),0.32(s,9H),-0.34(s,9H); 13 C NMR (100MHz, CDCl3, ppm): δ=151.1,141.8,133.7,131.3,129.0,128.1,50.6,45.0,43.5,38.8,38.6,32.7,32.1,0.8,-0.7.HRMS calcd forC 19 H 32 ClSi2[M+H] + 351.1726; found:351.1737.

[0056] The structure, NMR and high-resolution mass spectrometry data of the product obtained in Example 8 are as follows:

[0057] 1 H NMR (400MHz, CDCl3, ppm): δ = 7.31 (d, J = 8.8Hz, 1H), 6.96 (d, J = 2.8Hz, 1H), 6.82-6 .85(m,1H),3.78(s,3H),3.10(d,J=10.0Hz,1H),2.34(d,J=4.4Hz,1H),2.27(d,J= 3.2Hz,1H),1.94(d,J=10.0Hz,1H),1.72-1.77(m,1H),1.55-1.61(m,1H),1.40-1 .43(m,1H),1.34(d,J=10.4Hz,2H),1.22-1.25(m,2H),0.32(s,9H),-0.35(s,9H); 13 HRMS calcd for C 20 H35 OSi2[M+H] + 347.2221; found:347.2218.

[0058] The structure, NMR and high-resolution mass spectrometry data of the product obtained in Example 9 are as follows:

[0059] 1 H NMR (400MHz, CDCl3, ppm): δ = 7.26 (d, J = 8.4Hz, 1H), 6.83 (d, J = 2.8Hz, 1H), 6.71-6.74 (m, 1H), 3.07 (d, J = 10.0Hz, 1H), 2.82-2.90 (m, 6H), 1.94 ( d,J=8.8Hz,1H),1.70-1.76(m,1H),1.54-1.60(m,1H),1.39-1.42(m,1H) ),1.32(d,J=9.6Hz,2H),1.20-1.23(m,1H),0.32(s,9H),-0.34(s,9H); 13 HRMS calcdfor C 21 H 38 NSi2[M+H] + 360.2538; found:360.2536.

[0060] The structure, NMR and high-resolution mass spectrometry data of the product obtained in Example 10 are as follows:

[0061] 1 H NMR (400MHz, CDCl3, ppm): δ = 7.31-7.34 (m, 1H), 7.05-7.09 (m, 2H), 3.46 (d, J = 11.2Hz, 1H), 2.68 (s, 1H), 2.49 (s, 3H), 2.35 (d, J = 4.4Hz, 1H), 1.9 6(d,J=10.0Hz,1H),1.80-1.84(m,1H),1.55-1.61(m,1H),1.47-1.50(m ,1H),1.40-1.43(m,2H),1.31-1.34(m,1H),0.34(s,9H),-0.40(s,9H); 13HRMS calcdfor C 20 H 35 Si2[M+H] + 331.2272; found:331.2265.

[0062] The structure, NMR and high-resolution mass spectrometry data of the product obtained in Example 11 are as follows:

[0063] 1 H NMR (400MHz, CDCl3, ppm): δ = 7.29 (d, J = 7.6Hz, 1H), 7.20 (s, 1H), 6.95 (d, J = 7.6Hz, 1H), 3.13 (d, J = 10.4Hz, 1H), 2.35 (d, J = 5.2Hz, 1H), 2.29-2.33 (m, 4 H),1.99(d,J=10.0Hz,1H),1.72-1.76(m,1H),1.56-1.62(m,1H),1.41-1.4 4(m,1H),1.35-1.38(m,2H),1.24-1.27(m,2H),0.31(s,9H),-0.37(s,9H); 13 HRMS calcd for C 20 H 35 Si2[M+H] + 331.2272; found:331.2269. References: 1. Sore, H.; Galloway, W. et al. Palladium Catalysed Cross-Coupling of Organosilicon Reagents. Chem. Soc. Rev., 2012, 41, 1845-1866. 2.Ramesh,R.;Reddy,D.et al.Quest for Novel Chemical Entities throughIncorporation of Silicon in Drug Scaffolds.J.Med.Chem.,2018,61,3779-3798. 3.Xun,Q.;Xun,B.et al.Application of SiC Power Electronic Devices inSecondary Power Source for Aircraft.Renewable and Sustainable EnergyReviews.,2017,70,1336-1342. 4.Blakemore,D.;Castro,L.et al.Organic Synthesis ProvidesOpportunities to Transform Drug Discovery.Nat.Chem.,2018,10,383-394. 5.Zhou,G.;Guo,Z.et al.Divergent Synthesis of Fluoroalkyl Ketonesthrough Controlling the Reactivity of OrganoboronateComplexes.J.Am.Chem.Soc.,2024,146,4026-4035. 6.Gu,Y.;Shen,Y.et al.AMild and Direct Site-Selective sp 2 C-HSilylation of(Poly)Azines.J.Am.Chem.Soc.,2019,141(1):127-132. 7.Mortensen,M.;Husmann,R.et al.Synthesis and Applications ofSilicon-Containingα-Amino Acids.Chem.Soc.Rev.,2009,38(4):1002-1010. 8.Shirakawa,E.;Kurahashi,T.et al.Diphenylphosphinophenolate:A Ligandfor the Palladium-Catalysed Silylation of Aryl Halides ActivatingSimultaneously Both Palladium and Silicon.Chem.Commun.,2000,1895-1896. 9.Sakurai,H.;Kamiyama,Y.et al.The Palladium Complex-CatalyzedReactions of Hexaorganodisilanes with Dienes.Chem.Lett.,1975,4(8):887-890. 10.Tobisu,M.;Kita,Y.et al.Rhodium-Catalyzed Silylation andIntramolecular Arylation of Nitriles via the Silicon-Assisted Cleavage ofCarbon-Cyano Bonds.J.Am.Chem.Soc.,2008,130(47):15982-15989. 11.Lu,A.;Ji,X.et al.Palladium-Catalyzed C-H Silylation throughPalladacycles Generated from Aryl Halides.Angew.Chem.Int.Ed.,2018,57(12):3233-3237. 12.Ansell,M.;Roberts,D.et al.Synthesis of an[(NHC)2Pd(SiMe3)2]Complexand Catalytic cis-Bis(silyl)ations of Alkynes with UnactivatedDisilanes.Angew.Chem.Int.Ed.,2015,54(19):5578-5582。

Claims

1. A method for preparing a norbornene-containing arylsilane compound, comprising the following steps: Add the compound of formula I, compound A, compound B, catalyst and solvent into a pressure tube, fill with argon, react at 110-120°C for 5 hours, and monitor the reaction progress by thin layer chromatography until the reaction is complete. Extract with ethyl acetate and saturated brine, dry with anhydrous sodium sulfate, evaporate the solvent under reduced pressure, and separate and purify the residue by silica gel column chromatography using petroleum ether / ethyl acetate as mobile phase to obtain compound II. The reaction equation is as follows: In the formula: R is a hydrogen atom, a methyl group, an ethyl group, a tert-butyl group, a phenyl group, a chlorine group, a fluorine group, a methoxy group, or an N,N-dimethyl group.

2. The method for preparing a norbornene-containing arylsilane compound according to claim 1, characterized in that: The molar ratio of compound I to compound A, compound B and catalyst is 1:2.0-3.0:2.0-3.0:0.

1.

3. The method for preparing a norbornene-containing arylsilane compound according to claim 1, characterized in that: The reaction temperature is 110-120°C.

4. The method for preparing a norbornene-containing arylsilane compound according to claim 1, characterized in that: The catalyst is palladium acetate, bis(triphenylphosphine)palladium dichloride, or tetrakis(triphenylphosphine)palladium.

5. The method for preparing a norbornene-containing arylsilane compound according to claim 1, characterized in that: The ligand is triphenylphosphine, bis(diphenylphosphino)methane, or 1,4-bis(diphenylphosphino)butane.

6. The method for preparing a norbornene-containing arylsilane compound according to claim 1, characterized in that: The solvent is acetonitrile, tetrahydrofuran, toluene, and N,N-dimethylformamide.

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