Method for synthesizing silicon-group-containing tetra-substituted olefin compound through nickel catalysis

Abstract

The invention discloses a method for synthesizing a silicon-group-containing tetra-substituted olefin compound through nickel catalysis, and belongs to the technical field of organic synthesis. According to the invention, nickel is adopted to catalyze a cascade reaction of three components of alkynyl silane, aryl iodide and an organic aluminum reagent, migration and insertion of alkyne by an aryl nickel intermediate are regulated and controlled through an alpha silicon-based effect to form an alkenyl nickel intermediate, and a metal conversion reaction is further carried out; two functional groups are successfully introduced into alkynyl to construct a series of silicon-containing tetra-substituted olefin compounds, the application of an organic aluminum reagent in a three-component coupling reaction is expanded, and a new method is provided for high-regioselectivity synthesis of tetra-substituted olefin.

Description

Technical Field

[0001] This invention belongs to the field of organic synthesis technology, specifically relating to a method for preparing a silicon-containing tetrasubstituted olefin compound. This research was supported by the National Natural Science Foundation of China (22371269). Background Technology

[0002] For a long time, Negishi coupling reactions have primarily used organozinc reagents, mainly because they possess excellent functional group compatibility, exhibit good regioselectivity and stereoselectivity, do not require the addition of additional activators, and are compatible with a variety of catalysts and ligands. However, while aluminum is the most abundant metallic element in the Earth's crust and organoaluminum reagents are simple to prepare, their application in coupling reactions has long been overlooked due to their low selectivity.

[0003] Coupling reactions involving organoaluminum reagents mainly focus on two-component coupling. Since the first olefin coupling reaction involving organoaluminum reagents was reported by Negishi's group in 1976, coupling reactions of organoaluminum reagents with alkyl, alkenyl, alkynyl, aryl, carbonyl, silyl, and dialkylamino groups have been developed (Negishi, E.-IJ Am. Chem. Soc. 1976, 98, 6729−6731.). However, three-component reactions involving organoaluminum reagents are rare. So far, the following have been achieved: a three-component coupling reaction of trimethylaluminum, alkynes, and allyl alcohol (Yu Zhao. Angew. Chem. Int. Ed. 2020, 59, 14404-14408.); a carbonylation cross-coupling reaction of allyl alcohol with organoaluminum (Yifeng Chen. Angew. Chem. Int. Ed. 2022, 61, e202210484); a carbonylation cross-coupling reaction of aryl halides with organoaluminum reagents (Xiao-FengWu. Org. Lett. 2019, 21, 7624-7629.); and a dicarbonylation cross-coupling reaction of aryl halides with organoaluminum reagents (Xiao-Feng Wu. Org. Lett. 2020, 22, 636-641.).

[0004] Tetrasubstituted alkenes are widely found in natural product molecules, drug molecules, and bioactive molecules. In materials science, the structure of olefins can significantly affect the physicochemical properties of materials, thus their applications in organic conductive materials and organic light-emitting materials are constantly expanding. Traditional methods for synthesizing tetrasubstituted alkenes include metal coupling reactions, olefination reactions, olefin metathesis reactions, and elimination reactions. However, these synthetic methods face problems such as difficulties in precursor synthesis, low atom economy, difficulty in controlling E / Z configuration, and harsh reaction conditions. In recent years, transition metal-catalyzed alkyne bifunctionalization reactions have provided a novel route for constructing tetrasubstituted alkenes. However, the reaction substrates are generally limited to symmetrical alkynes and asymmetrical alkynes with directing groups; otherwise, the regioselectivity cannot be controlled. Summary of the Invention

[0005] To address the aforementioned synthetic challenges, this invention provides a nickel-catalyzed method for synthesizing silicon-containing tetrasubstituted olefin compounds. This invention employs a nickel-catalyzed three-component tandem reaction of an alkynylsilane, an aryl iodide, and an organoaluminum reagent. Through the α-silyl effect, the aryl nickel intermediate is regulated to induce the migration and insertion of the aryl nickel intermediate into the alkyne, forming an alkenyl nickel intermediate, which further undergoes a transfer metallization reaction. This successfully introduces two functional groups onto the alkynyl group to construct a series of silicon-containing tetrasubstituted olefin compounds, expanding the application of organoaluminum reagents in three-component coupling reactions and providing a novel method for the highly regioselective synthesis of tetrasubstituted olefins.

[0006] The present invention discloses a method for the nickel-catalyzed synthesis of silicon-containing tetrasubstituted olefin compounds, which adopts a one-step method to obtain the target product, specifically including the following steps:

[0007] Under nitrogen protection, alkynylsilane, aryl iodide, and organoaluminum reagent were thoroughly mixed in a solvent system in the presence of a nickel catalyst and a bifunctionalization reaction was carried out at 30-40 °C for 12-24 h. After the reaction was completed and cooled to room temperature, ethyl acetate was added for dilution, and the aluminum reagent was quenched with water and 1 mol / L dilute hydrochloric acid. The mixture was then extracted with ethyl acetate and saturated brine. The resulting organic phase was dried and the solvent was removed using a rotary evaporator. The residue was then separated by column chromatography or preparative high-performance liquid chromatography to obtain the target product.

[0008] The organoaluminum reagent is an alkenyl aluminum reagent. or aryl aluminum reagent .

[0009] When the organoaluminum reagent is an arylaluminum reagent At that time, the reaction system also included KF.

[0010] The reaction route is shown below:

[0011]

[0012] In the formula, substituent Ar is selected from substituted or unsubstituted aryl groups, Ar' is selected from substituted or unsubstituted aryl groups, R is selected from one or more of aryl, alkyl, and hydrogen groups, and R 1 It is selected from substituted or unsubstituted aryl, substituted or unsubstituted alkyl, and cycloalkyl; the substituent used for substitution is selected from one or more of C1-C6 alkyl, C1-C6 alkoxy, halogen, and C1-C6 alkoxycarbonyl.

[0013] The nickel catalyst is nickel(II) ditriphenylphosphine dichloride.

[0014] The solvent is dry diethyl ether, or a mixture of dry tert-butyl methyl ether and dry cyclopentyl methyl ether, or a mixture of dry diethyl ether and dry 1,4-dioxane, or a mixture of dry ethylene glycol dimethyl ether and dry n-hexane, with a volume ratio controlled at 1:0.4~0.6.

[0015] The molar ratio of alkynylsilane, aryl iodide and organoaluminum reagent is controlled to be 1:2~3:2~3.

[0016] The molar ratio of alkynylsilane and potassium fluoride is controlled at 1:1.

[0017] The structural formulas of the silicon-containing tetrasubstituted olefin compounds prepared by the method of the present invention include the following:

[0018]

[0019] This invention employs a one-step synthesis method, utilizing a nickel catalyst, to achieve the synthesis of silicon-containing tetrasubstituted olefin compounds. The system is simple, the reaction conditions are mild, and the target product can be obtained without additional treatment. This method is easy to operate, has broad substrate applicability, and the product exhibits good regioselectivity, demonstrating economic practicality and promising prospects for industrial production. Detailed Implementation

[0020] The technical solution of the present invention will be further analyzed and explained through specific embodiments below.

[0021] Filtering by criteria (Part 1)

[0022] Prepare a clean, dry 10 ml Shrek tube with a suitable magnetic magnet. In a glove box, add 0.008 mmol of bis(triphenylphosphine) nickel(II) dichloride to the Shrek tube. Vacuum the tube three times under double-row conditions to ensure the side arm is also under nitrogen atmosphere. Under a nitrogen flow, sequentially add 0.2 mmol of alkynylsilane, 0.4 mmol of iodobenzene, and 0.4 mmol of alkenylaluminum reagent (0.4 mmol, 0.4 ml solvent) to the 10 ml Shrek tube. 2 ) and solvent 1(1 ml), after addition, the mixture was stirred at 40 °C for 12 h. After the reaction was complete and cooled to room temperature, ethyl acetate was added for dilution. The aluminum reagent was quenched with water and 1 mol / L dilute hydrochloric acid. Extraction was performed with ethyl acetate and saturated brine. The resulting organic phase was dried and the solvent was removed using a rotary evaporator. The product was analyzed by 1H NMR spectroscopy. The yield was calculated by adding a quantitative internal standard of 1,1,2,2-dichloroethane and comparing the characteristic peak areas of the NMR spectrum. The nickel catalyst and solvent were screened. 1 and solvent 2 Find the optimal reaction conditions.

[0023]

[0024]

[0025] *The solvent is composed of solvent 1 and solvent 2 The mixture is composed of two components with a volume ratio of 1:0.4.

[0026] When using a three-component coupling of phenylethynyltrimethylsilane and iodobenzene with terminal alkyl-terminated alkenyl aluminum reagent, the optimal solvents were determined to be diethyl ether and 1,4-dioxane after screening.

[0027]

[0028] Through screening of nickel catalysts, bis(triphenylphosphine) nickel dichloride (II) was found to be the most effective.

[0029] Conditional Filtering (Part Two)

[0030] Prepare a clean, dry 10 ml Shrek tube with a suitable magnetic magnet. In a glove box, add 0.008 mmol of bis(triphenylphosphine) nickel(II) dichloride to the Shrek tube. Vacuum the tube three times under double-row conditions to ensure the side arm is also under nitrogen atmosphere. Under a nitrogen flow, sequentially add 0.2 mmol of alkynylsilane, 0.4 mmol of iodobenzene, and 0.4 mmol of alkenylaluminum reagent (0.4 mmol, 0.4 ml solvent) to the 10 ml Shrek tube. 2 ) and solvent 1 (1 ml) After addition, the mixture was stirred at 30 °C for 12 h. The yield was calculated by adding a quantitative internal standard 1,1,2,2-dichloroethane and comparing the characteristic peak areas of the NMR spectra. The optimal reaction conditions were determined by screening solvent 1 and solvent 2.

[0031]

[0032]

[0033] *The solvent is composed of solvent1 and solvent 2 The mixture is composed of two components with a volume ratio of 1:0.4.

[0034] When using a three-component coupling of phenylethynylsilane containing silane and iodobenzene with terminal alkyl-terminated alkenyl aluminum reagent as raw materials, the optimal solvents were determined to be tert-butyl methyl ether and cyclopentyl methyl ether after screening.

[0035] Filtering by criteria (Part 3)

[0036] Prepare a clean, dry 10 ml Shrek tube with a suitable-sized magnetic magnet. Vacuum the tube three times under double-row tube conditions to create a nitrogen atmosphere. Under a nitrogen flow, add 0.2 mmol of alkynylsilane, 0.6 mmol of iodobenzene, and 0.6 mmol of alkenylaluminum reagent (0.6 mmol, 0.6 ml of solvent) sequentially to the 10 ml Shrek tube. 2 ) and solvent 1 (1 ml) After addition, the mixture was stirred at 30 °C for 24 h. The yield was calculated by adding a quantitative internal standard 1,1,2,2-dichloroethane and comparing the characteristic peak areas of the NMR spectra. The optimal reaction conditions were determined by screening substrate equivalents, temperature, solvent 1, and solvent 2. Since nickel(II) ditriphenylphosphine dichloride was added during the preparation of the aryl-terminated alkenyl aluminum reagent, no additional nickel catalyst was added for this reaction.

[0037]

[0038]

[0039] When using an aryl-terminated alkenylaluminate reagent to couple with an alkynylsilane and an iodobenzene tricomponent, the optimal equivalent of the substrate equivalence and iodobenzene was determined to be 3.0 equivalents; the optimal temperature was determined to be 30°C; and the optimal solvent was determined to be diethyl ether.

[0040] Conditional Filtering (Part 4)

[0041] Prepare a clean, dry 10 ml Shrek tube with a suitable-sized magnetic magnet. In a glove box, add 0.016 mmol of nickel(II) ditriphenylphosphine dichloride and 0.2 mmol of potassium fluoride to the Shrek tube. Vacuum the tube three times under a double-row tube arrangement to ensure the side arm is also under nitrogen. Under a nitrogen flow, add 0.2 mmol of alkynylsilane, 0.6 mmol of iodobenzene, 0.6 mmol of alkenylaluminum reagent (0.6 mmol, 0.6 ml solvent), and 1 ml of solvent sequentially to the 10 ml Shrek tube. After addition, stir at 30 °C for 12 h. The yield was calculated by adding a quantitative internal standard, mesitylene, and comparing the characteristic peak areas of the NMR spectra. Optimal reaction conditions were determined by screening solvents and fluoride salts.

[0042]

[0043]

[0044] When using aryl aluminum reagents to couple with alkynyl silane and iodobenzene, solvent screening determined that ethylene glycol dimethyl ether was the optimal solvent; and fluoride screening determined that potassium fluoride was the optimal fluoride salt.

[0045] Synthetic routes for alkynylsilane substrates:

[0046]

[0047] Method 1: Place a suitable magnetic ball into a 250 ml round-bottom flask, dry the flask thoroughly in an oven, and stopper it with a rubber stopper to cool. Vacuum the flask three times under a double-row tube to create a nitrogen atmosphere. Add tetrahydrofuran and phenylacetylene. Then place the flask in a -78 °C cryogenic reactor and add n-butyllithium (1.1 equiv) dropwise, continuing the reaction at this temperature for 1 h. Next, add chlorosilane dropwise to the solution, gradually raising the temperature from -78 °C to room temperature, monitoring the reaction by TLC until completion. After the reaction is complete, quench with saturated ammonium chloride solution, followed by extraction, drying, filtration, concentration, and column chromatography to obtain the target alkynylsilane substrate.

[0048] Method 2: Place a suitable magnetic ball into a 250 ml round-bottom flask, dry the flask thoroughly in an oven, and stopper it with a rubber stopper to cool. Add bis(triphenylphosphine)palladium dichloride (2 mol%) and cuprous iodide (3 mol%) to the round-bottom flask, and evacuate the gas three times under double-row tubes to create a nitrogen atmosphere. Add triethylamine and the aryl iodide. Then place the flask on a magnetic stirrer and add ethynyltrimethylsilane (1.2 equiv) dropwise while stirring. Continue the reaction at room temperature and monitor the reaction with TLC until completion. After the reaction is complete, extract with saturated ammonium chloride solution and ethyl acetate, dry, filter through a vacuum funnel containing silica gel and diatomaceous earth, concentrate the filtrate, and separate by column chromatography to obtain the target ethynylsilane substrate.

[0049] Method 1 is applicable to substrates with different substituents on a silicon-based substrate; Method 2 is applicable to substrates with different substituents on a benzene ring.

[0050] Synthetic route of alkenyl aluminum reagents:

[0051]

[0052] Method 1: Place a suitable magnetic ball into a 25 ml Shrek tube, dry the Shrek tube thoroughly in an oven, screw on the stopper, and let it cool. Vacuum the tube three times under a double-row tube to create a nitrogen atmosphere. Add alkyl alkyne (4 mmol, 1.0 eq) under a nitrogen flow, then add DIBAL-H dropwise (4 mmol, 4 ml, 1.0 M in hexane, 1.0 eq). Gradually heat the reaction system to 55 °C and react at this temperature for 4 h. Use an external oil pump to remove the hexane solvent under a cold trap, and prepare a solution of 4 ml of 1,4-dioxane or cyclopentyl methyl ether as needed.

[0053] Method 2: Place a suitable magnetic ball into a 25 ml Shrek tube, dry the Shrek tube thoroughly in an oven, screw on the stopper, and let it cool. Add 0.12 mmol (3 mol%) of nickel(II) ditriphenylphosphine dichloride to the Shrek tube in a glove box. Vacuum the tube three times under a double-row tube to ensure the side arm is also in a nitrogen atmosphere. Add THF (2.6 ml) under a nitrogen flow, cool to 0 °C to allow the nickel catalyst to fully dissolve, then add DIBAL-H (4 mmol, 4 ml, 1.0 M inhexane, 1.0 eq) and aryl alkynes (4 mmol, 1.0 eq) dropwise. Gradually heat the reaction system to 22 °C and react at this temperature for 2 h. Use an external oil pump to remove the hexane and THF solvent under a cold trap, and prepare a 4 ml solution of diethyl ether as needed.

[0054] Method 1 is applicable to alkenyl aluminum reagents with alkyl groups at the end; Method 2 is applicable to alkenyl aluminum reagents with aryl groups at the end.

[0055] Synthetic route of aryl aluminum reagents:

[0056]

[0057] Place a suitable magnetic ball into a 100 ml round-bottom flask, dry the flask thoroughly in an oven, and stopper it with a rubber stopper to cool. Vacuum the flask three times under double-row tubes to create a nitrogen atmosphere. Add the aryl Grignard reagent (1.0 min THF). Then place the flask in a 0 °C ice-water bath and add diisobutylaluminum chloride (1.0 M in hexane) dropwise. Gradually raise the temperature to room temperature and stir overnight. Filter the magnesium salt produced in the reaction using a glove box, and wash the residue three times with n-hexane. Dry the filtrate under an oil pump connected to a cold trap, and dissolve the residue in 1.0 M n-hexane.

[0058] Example 1: (E)-(1,1-diphenyloct-1,3-dien-2-yl)trimethylsilane

[0059]

[0060] Prepare a clean and dry 10 ml Shrek tube with a suitable magnetic magnet. In a glove box, add 0.008 mmol of bis(triphenylphosphine) nickel(II) dichloride to the Shrek tube. Vacuum the tube three times under a double-row tube arrangement to ensure the side arm is also under nitrogen. Under a nitrogen flow, add 1a (0.2 mmol), 2a (0.4 mmol), 3a (0.4 mmol, 0.4 ml), and ether (1 ml) sequentially to the 10 ml Shrek tube. After addition, stir at 40 °C for 12 h. After the reaction is complete and cooled to room temperature, dilute with ethyl acetate. Quench the aluminum reagent with water and 1 mol / L dilute hydrochloric acid. Extract with ethyl acetate and saturated brine. Dry the resulting organic phase and remove the solvent using a rotary evaporator. Separate the residue using preparative high-performance liquid chromatography (HPLC) to obtain the target product 4a, a yellow oily liquid, with a 76% yield and a regioselectivity of 92:8.

[0061] By nuclear magnetic resonance hydrogen spectrum ( 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 The chemical shift and fragmentation of the yellow oily liquid product were analyzed by C NMR, and the molecular weight was determined by high-resolution mass spectrometry (HRMS). 1H NMR (400 MHz, CDCl3)δ 7.28-7.19 (m, 5H), 7.18-7.13 (m, 3H), 7.11 (m, 2H), 6.14 (dt, J = 16.0, 1.5Hz, 1H), 5.41 (dt, J = 16.0, 7.0 Hz, 1H), 1.92 (dq, J = 7.0, 1.5 Hz, 2H), 1.28-1.06 (m, 4H), 0.82 (t, J = 7.1 Hz, 3H), -0.11 (s, 9H). 13 C NMR (101 MHz, CDCl3) δ 153.1, 145.3, 144.1, 140.0, 133.2, 132.8, 130.0, 130.0, 127.9,127.8, 127.2, 126.4, 33.2, 31.7, 22.2, 14.1, 1.2. HRMS (ESI) (m / z): Calcd forC 23 H 30 NaSi [M+Na] + : 357.2014, found: 347.2013. This proves that the yellow oily liquid product obtained from the above reaction is (E)-(1,1-diphenyloct-1,3-dien-2-yl)trimethylsilane.

[0062] Example 2: Preparation of (E)-(1,1-diphenyldec-1,3-dien-2-yl)trimethylsilane

[0063]

[0064] 1a, 2a, and 3b were used as starting substrates to prepare target product 4b, and the preparation method was basically the same as the operation steps in Example 1. The product was a yellow oily liquid with a yield of 53%.

[0065] By nuclear magnetic resonance hydrogen spectrum ( 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 The chemical shift and fragmentation of the yellow oily liquid product were analyzed by C NMR, and the molecular weight was determined by high-resolution mass spectrometry (HRMS). 1H NMR (400 MHz, CDCl3)δ 7.28-7.19 (m, 5H), 7.18-7.14 (m, 3H), 7.13-7.09 (m, 2H), 6.14 (dt, J =16.0, 1.4 Hz, 1H), 5.42 (dt, J = 16.0, 7.0 Hz, 1H), 1.92 (dq, J = 7.0, 1.4Hz, 2H), 1.36-1.05 (m, 8H), 0.86 (t, J = 7.0 Hz, 3H), -0.11 (s, 9H). 13 C NMR(101 MHz, CDCl3) δ 153.0, 145.3, 144.1, 139.9, 133.3, 132.8, 130.0, 130.0,127.9, 127.8, 127.2, 126.4, 33.6, 31.9, 29.5, 28.9, 22.8, 14.3, 1.2. HRMS(ESI) (m / z): Calcd for C 25 H 35 Si [M+H] + : 363.2508, found: 363.2518. This proves that the yellow oily liquid product obtained from the above reaction is (E)-(1,1-diphenyldec-1,3-dien-2-yl)trimethylsilane.

[0066] Example 3: Preparation of (E)-(4-cyclopropyl-1,1-diphenylbut-1,3-dien-2-yl)trimethylsilane

[0067]

[0068] 1a, 2a, and 3c were used as starting substrates to prepare the target product 4c, and the preparation method was basically the same as the operation steps in Example 1. The product was a yellow oily liquid with a yield of 63% and a regioselectivity greater than 20:1.

[0069] By nuclear magnetic resonance hydrogen spectrum ( 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 The chemical shift and fragmentation of the yellow oily liquid product were analyzed by C NMR, and the molecular weight was determined by high-resolution mass spectrometry (HRMS). 1H NMR (400 MHz, CDCl3)δ 7.24 (m, 5H), 7.19-7.09 (m, 5H), 6.29 (d, J = 16.0 Hz, 1H), 5.01 (dd, J =16.0, 8.6 Hz, 1H), 1.33-1.19 (m, 1H), 0.65-0.58 (m, 2H), 0.24-0.18 (m, 2H), -0.11 (s, 9H). 13 HRMS (ESI)(m / z): Calcd for C 22 H 26 NaSi [M+Na] + : 341.1701, found: 341.1704. This proves that the yellow oily liquid product obtained from the above reaction is (E)-(4-cyclopropyl-1,1-diphenylbut-1,3-dien-2-yl)trimethylsilane.

[0070] Example 4: Preparation of (E)-(1,1-diphenyloct-1,3-dien-2-yl)dimethyl(phenyl)silane

[0071]

[0072] 1b, 2a, and 3a were used as starting substrates to prepare the target product 4d, and the preparation method was basically the same as the operation steps in Example 1. The product was a yellow oily liquid with a yield of 54% and a regioselectivity of 92:8.

[0073] By nuclear magnetic resonance hydrogen spectrum ( 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 The chemical shift and fragmentation of the yellow oily liquid product were analyzed by C NMR, and the molecular weight was determined by high-resolution mass spectrometry (HRMS). 1H NMR (400 MHz, CDCl3)δ 7.53-7.46 (m, 2H), 7.33-7.27 (m, 3H), 7.24-7.20 (m,2H), 7.18-7.11 (m, 6H),7.11-7.07 (m, 2H), 6.12 (dt, J = 16.0, 1.5 Hz, 1H), 5.33 (dt, J = 16.0, 7.0Hz, 1H), 1.82 (dq, J = 7.0, 1.5 Hz, 2H), 1.19-1.00 (m, 4H), 0.81-0.67 (t, J =7.0 Hz, 3H), 0.01 (s, 9H). 13 C NMR (101 MHz, CDCl3) δ 154.8, 145.0, 144.1,141.3, 137.6, 134.7, 133.9, 132.8, 130.2, 130.1, 128.5, 127.9, 127.9, 127.7,127.4, 126.6, 33.2, 31.5, 22.1, 14.1, 0.0. HRMS (ESI) (m / z): Calcd forC 28 H 33 Si [M+H] + : 397.2352, found: 397.2342. This proves that the yellow oily liquid product obtained from the above reaction is (E)-(1,1-diphenyloct-1,3-dien-2-yl)dimethyl(phenyl)silane.

[0074] Example 5: (E)-(1,1-diphenyloct-1,3-dien-2-yl)dimethylsilane

[0075]

[0076] Prepare a clean and dry 10 ml Shrek tube with a suitable magnetic magnet. In a glove box, add 0.008 mmol of bis(triphenylphosphine) nickel(II) dichloride to the Shrek tube. Vacuum the tube three times under a double-row tube arrangement to ensure the side arm is also under nitrogen. Under a nitrogen flow, add 1c (0.2 mmol), 2a (0.4 mmol), 3d (0.4 mmol, 0.4 ml), and tert-butyl methyl ether (1 ml) sequentially to the 10 ml Shrek tube. After addition, stir at 30 °C for 12 h. After the reaction is complete and cooled to room temperature, dilute with ethyl acetate. Quench the aluminum reagent with water and 1 mol / L dilute hydrochloric acid. Extract with ethyl acetate and saturated brine. Dry the resulting organic phase and remove the solvent using a rotary evaporator. Separate the residue using preparative high-performance liquid chromatography (HPLC) to obtain the target product 4e, a yellow oily liquid, with a 50% yield and a regioselectivity greater than 20:1.

[0077] By nuclear magnetic resonance hydrogen spectrum ( 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 The chemical shift and fragmentation of the yellow oily liquid product were analyzed by C NMR, and the molecular weight was determined by high-resolution mass spectrometry (HRMS). 1 H NMR (600 MHz, CDCl3)δ 7.34-7.28 (m, 5H), 7.27-7.23 (m, 1H), 7.18 (m, 4H), 6.31 (dt, J = 16.0, 1.5Hz, 1H), 5.89 (dt, J = 16.0, 7.0 Hz, 1H), 4.10 (h, J = 3.9 Hz, 1H), 2.06 (dq,J = 7.0, 1.5 Hz, 2H), 1.41-1.27 (m, 4H), 0.91 (t, J = 7.1 Hz, 3H), 0.09 (d, J= 3.9 Hz, 6H). 13 C NMR (151 MHz, CDCl3) δ 153.8, 145.1, 143.2, 136.4, 133.9,133.2, 130.3, 130.0, 127.9, 127.3, 126.9, 33.5, 31.8, 22.3, 14.1, -2.3. HRMS(ESI) (m / z): Calcd for C 22 H 28 NaSi [M+Na] +: 343.1858, found: 343.1853. This proves that the yellow oily liquid product obtained from the above reaction is (E)-(1,1-diphenyloct-1,3-dien-2-yl)dimethylsilane.

[0078] Example 6: Preparation of (E)-(1,1-diphenyloct-1,3-dien-2-yl)(methyl)(phenyl)silane

[0079]

[0080] The target product 4f was prepared using 1d, 2a, and 3d as starting substrates, following essentially the same procedure as in Example 5. The product was a yellow oily liquid with a yield of 50% and a regioselectivity greater than 20:1.

[0081] By nuclear magnetic resonance hydrogen spectrum ( 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 The chemical shift and fragmentation of the yellow oily liquid product were analyzed by C NMR, and the molecular weight was determined by high-resolution mass spectrometry (HRMS). 1 H NMR (600 MHz, CDCl3)δ 7.53 (m, 2H), 7.37-7.26 (m, 5H), 7.25-7.14 (m, 6H), 7.12-7.05 (m, 2H), 6.33(dt, J = 16.1, 1.5 Hz, 1H), 5.81 (dt, J = 16.1, 7.0 Hz, 1H), 4.50 (q, J = 4.0Hz, 1H), 1.95 (dq, J = 7.0, 1.5 Hz, 2H), 1.27 – 1.09 (m, 4H), 0.81 (t, J =7.0 Hz, 3H), 0.23 (d, J = 4.0 Hz, 3H). 13 C NMR (151 MHz, CDCl3) δ 155.4,144.8, 143.2, 137.3, 135.2, 134.6, 134.3, 133.1, 130.4, 130.0, 129.0, 127.9,127.9, 127.8, 127.4, 127.1, 33.4, 31.6, 22.2, 14.0, -4.4. HRMS (ESI) (m / z):Calcd for C 27 H 30 NaSi [M+Na] +: 405.2014, found: 405.2009. This proves that the yellow oily liquid product obtained from the above reaction is (E)-(1,1-diphenyloct-1,3-dien-2-yl)(methyl)(phenyl)silane.

[0082] Example 7: Preparation of (E)-(1,1-diphenyloct-1,3-dien-2-yl)diphenylsilane

[0083]

[0084] 1e, 2a, and 3d were used as starting substrates to prepare 4g of the target product, and the preparation method was basically the same as the operation steps in Example 5. The product was a yellow oily liquid with a yield of 51% and a regioselectivity of 94:6.

[0085] By nuclear magnetic resonance hydrogen spectrum ( 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 The chemical shift and fragmentation of the yellow oily liquid product were analyzed by C NMR, and the molecular weight was determined by high-resolution mass spectrometry (HRMS). 1 H NMR (600 MHz, CDCl3)δ 7.66-7.58 (m, 4H), 7.47-7.32 (m, 8H), 7.31-7.25 (m, 3H), 7.23-7.20 (m, 1H),7.20-7.16 (m, 2H), 7.16-7.12 (m, 2H), 6.37 (dd, J = 16.1, 1.3 Hz, 1H), 5.69 (dt, J = 16.1, 7.1 Hz, 1H), 1.88 (dq, J = 7.1, 1.3 Hz, 2H), 1.08 (m, 4H), 0.78 (t, J = 6.9 Hz, 3H). 13 C NMR (151 MHz, CDCl3) δ 157.0, 144.6, 143.2,136.6, 135.8, 135.0, 133.0, 132.5, 130.4, 130.1, 129.3, 128.0, 127.9, 127.8,127.5, 127.3, 33.4, 31.4, 22.0, 14.0. HRMS (ESI) (m / z): Calcd for C 32 H 32 NaSi[M+Na] +: 467.2171, found: 467.2169. This proves that the yellow oily liquid product obtained from the above reaction is (E)-(1,1-diphenyloct-1,3-dien-2-yl)diphenylsilane.

[0086] Example 8: Preparation of (E)-(1,1,4-triphenylbut-1,3-dien-2-yl)trimethylsilane

[0087]

[0088] Prepare a clean, dry 10 ml Shrek tube with a suitable-sized magnetic magnet. Vacuum the tube three times under a double-row tube arrangement to create a nitrogen atmosphere. Under a nitrogen flow, add 1a (0.2 mmol), 2a (0.6 mmol), 3e (0.6 mmol, 0.6 ml), and diethyl ether (1 ml) sequentially to the 10 ml Shrek tube. After addition, stir at 30 °C for 24 h. After the reaction is complete and cooled to room temperature, dilute with ethyl acetate. Quench the aluminum reagent with water and 1 mol / L dilute hydrochloric acid. Extract with ethyl acetate and saturated brine. Dry the resulting organic phase and remove the solvent using a rotary evaporator. Separate the residue using preparative high-performance liquid chromatography (HPLC) to obtain a 73% yield of a 4 h yellow solid.

[0089] By nuclear magnetic resonance hydrogen spectrum ( 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 The chemical shift and splitting of the yellow solid product were analyzed by C NMR, and the molecular weight was determined by high-resolution mass spectrometry (HRMS). 1 H NMR (600 MHz, CDCl3) δ7.30 -7.25 (m, 4H), 7.25-7.21 (m, 3H), 7.21-7.12 (m, 8H), 7.01 (d, J = 16.5Hz, 1H), 6.44 (d, J = 16.5 Hz, 1H), -0.02 (s, 9H). 13 C NMR (151 MHz, CDCl3) δ 13 C NMR (151 MHz, CDCl3) δ 155.4, 145.1, 143.8, 139.3, 138.4, 133.3, 131.0,130.1, 130.0, 128.6, 128.0, 128.0, 127.6, 127.0, 127.0, 126.2, 1.5. HRMS(ESI) (m / z): Calcd for C 25 H 27Si [M+H] + : 355.1882, found: 355.1875. This proves that the yellow solid product obtained from the above reaction is (E)-(1,1,4-triphenylbut-1,3-dien-2-yl)trimethylsilane.

[0090] Example 9: Preparation of (E)-(1,1-bis([1,1'-biphenyl]-4-yl)-4-phenylbut-1,3-dien-2-yl)trimethylsilane

[0091]

[0092] 1f, 2b, and 3e were used as starting substrates to prepare the target product 4i, and the preparation method was basically the same as the operation steps in Example 8. A yellow solid was obtained, with a product yield of 86%.

[0093] By nuclear magnetic resonance hydrogen spectrum ( 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 The chemical shift and splitting of the yellow solid product were analyzed by C NMR, and the molecular weight was determined by high-resolution mass spectrometry (HRMS). 1 H NMR (600 MHz, CDCl3) δ7.71 -7.68 (m, 2H), 7.68-7.64 (m, 2H), 7.63 (m, J = 8.2 Hz, 2H), 7.61-7.56(m, 2H), 7.48 (dt, J = 13.4, 7.7 Hz, 4H), 7.43-7.38 (m, 6H), 7.39-7.33 (m,4H), 7.32-7.27 (m, 1H), 7.17 (d, J = 16.6 Hz, 1H), 6.58 (d, J = 16.6 Hz, 1H), 0.11 (s, 9H). 13 C NMR (151 MHz, CDCl3) δ 154.6, 144.2, 142.7, 140.8, 140.4,139.9, 139.7, 138.4, 133.4, 131.2, 130.9, 130.7, 128.9, 128.9, 128.7, 127.5,127.4, 127.2, 127.1, 127.1, 126.7, 126.6, 126.2, 1.7. HRMS (ESI) (m / z): Calcdfor C 37 H 35 Si [M+H] +: 507.2508, found: 507.2518. This proves that the yellow solid product obtained from the above reaction is (E)-(1,1-bis([1,1'-biphenyl]-4-yl)-4-phenylbut-1,3-dien-2-yl)trimethylsilane.

[0094] Example 10: Preparation of (E)-(1,1-bis(4-methoxyphenyl)-4-phenylbut-1,3-dien-2-yl)trimethylsilane

[0095]

[0096] 1g, 2c, and 3e were used as starting substrates to prepare the target product 4j, and the preparation method was basically the same as the operation steps in Example 8. The product was a yellow oily liquid with a yield of 77% and a regioselectivity of 72:28.

[0097] By nuclear magnetic resonance hydrogen spectrum ( 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 The chemical shift and fragmentation of the yellow oily liquid product were analyzed by C NMR, and the molecular weight was determined by high-resolution mass spectrometry (HRMS). 1 H NMR (600 MHz, CDCl3)δ 7.25-7.18 (m, 4H), 7.15-7.10 (m, 1H), 7.08-7.04 (m, 5H), 6.81 (d, J = 8.6Hz, 2H), 6.78 (d, J = 8.6 Hz, 2H), 6.46 (d, J = 16.6 Hz, 1H), 3.80 (s, 3H), 3.77 (s, 3H), -0.01 (s, 9H). 13 C NMR (151 MHz, CDCl3) δ 159.4, 158.7, 155.0,138.7, 138.2, 137.9, 136.5, 134.0, 131.9, 131.5, 130.3, 128.6, 126.8, 126.1,113.3, 113.3, 55.4, 55.3, 1.8. HRMS (ESI) (m / z): Calcd for C 27 H 31 O2Si [M+H] + :415.2093, found: 415.2084. This proves that the yellow oily liquid product obtained from the above reaction is (E)-(1,1-bis(4-methoxyphenyl)-4-phenylbut-1,3-dien-2-yl)trimethylsilane.

[0098] Example 11: Preparation of (E)-trimethyl(4-phenyl-1,1-di-p-tolylbut-1,3-dien-2-yl)trimethylsilane

[0099]

[0100] The target product 4k was prepared using 1h, 2d, and 3e as starting substrates, following essentially the same procedure as in Example 8. The product was a yellow solid with a yield of 77% and a regioselectivity of 87:13.

[0101] By nuclear magnetic resonance hydrogen spectrum ( 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 The chemical shift and splitting of the yellow solid product were analyzed by C NMR, and the molecular weight was determined by high-resolution mass spectrometry (HRMS). 1 H NMR (600 MHz, CDCl3) δ7.33 -7.23 (m, 4H), 7.20 (m, 1H), 7.17-7.02 (m, 9H), 6.51 (d, J = 16.6 Hz,1H), 2.40 (s, 3H), 2.36 (s, 3H), 0.04 (s, 9H). 13 C NMR (151 MHz, CDCl3) δ155.7, 142.6, 141.0, 138.6, 138.5, 137.2, 136.6, 133.8, 130.5, 130.2, 130.1,128.7, 128.6, 128.6, 126.9, 126.1, 21.4, 21.4, 1.7. HRMS (ESI) (m / z): Calcdfor C 27 H 30 NaSi [M+Na] + : 405.2014, found: 405.2014. This proves that the yellow solid product obtained from the above reaction is (E)-trimethyl(4-phenyl-1,1-di-p-tolylbut-1,3-dien-2-yl)trimethylsilane.

[0102] Example 12: Preparation of diethyl 4,4'-(4-phenyl-2-(trimethylsilyl)but-1,3-dien-1,1-2-yl)(E)-dibenzoate

[0103]

[0104] 1i, 2e, and 3e were used as starting substrates to prepare the target product 4l, and the preparation method was basically the same as the operation steps in Example 8. The product was a yellow oily liquid with a yield of 55%.

[0105] By nuclear magnetic resonance hydrogen spectrum ( 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 The chemical shift and fragmentation of the yellow oily liquid product were analyzed by C NMR, and the molecular weight was determined by high-resolution mass spectrometry (HRMS). 1 H NMR (600 MHz, CDCl3)δ 7.92 (d, J = 8.1 Hz, 2H), 7.85 (d, J = 8.1 Hz, 2H), 7.19 (m, 3H), 7.16-7.12(m, 3H), 7.13-7.08 (m, 3H), 6.86 (d, J = 16.5 Hz, 1H), 6.34 (d, J = 16.5 Hz,1H), 4.31 (q, J = 7.1 Hz, 2H), 4.27 (q, J = 7.1 Hz, 2H), 1.32 (t, J = 7.1 Hz,3H), 1.29 (t, J = 7.1 Hz, 3H), -0.08 (s, 9H). 13 C NMR (151 MHz, CDCl3) δ166.5, 166.5, 152.5, 149.0, 147.8, 142.4, 137.9, 132.4, 132.1, 130.1, 130.1,129.8, 129.5, 129.4, 129.1, 128.7, 127.4, 126.2, 61.2, 61.1, 14.5, 1.4. HRMS(ESI) (m / z): Calcd for C 31 H 34 NaO4Si [M+Na] + : 499.2305, found: 499.2304. This proves that the yellow oily liquid product obtained from the above reaction is 4,4'-(4-phenyl-2-(trimethylsilyl)but-1,3-dien-1,1-2-yl)(E)-dibenzoic acid diethyl ester.

[0106] Example 13: Preparation of (E)-(1,1-bis(4-fluorophenyl)-4-phenylbut-1,3-dien-2-yl)trimethylsilane

[0107]

[0108] 1j, 2f, and 3e were used as starting substrates to prepare the target product 4m, and the preparation method was basically the same as the operation steps in Example 8. The product was a yellow oily liquid with a yield of 58%.

[0109] By nuclear magnetic resonance hydrogen spectrum ( 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 The chemical shift and fragmentation of the yellow oily liquid product were analyzed by C NMR, and the molecular weight was determined by high-resolution mass spectrometry (HRMS). 1 H NMR (600 MHz, CDCl3)δ 7.33-7.27 (m, 2H), 7.26-7.20 (m, 3H), 7.20-7.13 (m, 4H), 7.05 (m, 2H),7.03-6.96 (m, 3H), 6.47 (d, J = 16.5 Hz, 1H), 0.04 (s, 9H). 13 C NMR (151 MHz, CDCl3) δ162.6 (d, J = 246.9 Hz), 161.9 (d, J = 246.7 Hz), 152.7, 141.0 (d, J= 3.2 Hz), 140.4, 139.5 (d, J = 3.3 Hz), 138.2, 132.8, 131.9 (d, J = 8.0 Hz), 131.7 (d, J = 8.0 Hz), 131.5, 128.7, 127.2, 126.2, 115.1 (d, J = 21.3 Hz), 115.0 (d, J = 21.3 Hz), 1.5. 19 F NMR (565 MHz, CDCl3) δ -114.4, -115.0. HRMS(ESI) (m / z): Calcd for C 25 H 25 F2Si [M+H] + : 391.1694, found: 391.1684. This proves that the yellow oily liquid product obtained from the above reaction is (E)-(1,1-bis(4-fluorophenyl)-4-phenylbut-1,3-dien-2-yl)trimethylsilane.

[0110] Example 14: Preparation of (E)-(4-phenyl-1,1-bis(4-(trifluoromethyl)phenyl)but-1,3-dien-2-yl)trimethylsilane

[0111]

[0112] The target product 4n was prepared using 1k, 2g, and 3e as starting substrates, following essentially the same procedure as in Example 8. The product was a yellow oily liquid with a yield of 40%.

[0113] By nuclear magnetic resonance hydrogen spectrum ( 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 The chemical shift and fragmentation of the yellow oily liquid product were analyzed by C NMR, and the molecular weight was determined by high-resolution mass spectrometry (HRMS). 1 H NMR (600 MHz, CDCl3)δ 7.59 (d, J = 8.0 Hz, 2H), 7.52 (d, J = 8.0 Hz, 2H), 7.34 – 7.29 (m, 2H),7.29-7.23 (m, 4H), 7.21-7.16 (m, 3H), 6.90 (d, J = 16.4 Hz, 1H), 6.41 (d, J =16.4 Hz, 1H), -0.01 (s, 9H). 13 C NMR (151 MHz, CDCl3) δ 151.3, 147.8, 146.6,143.0, 137.7, 132.8, 131.8, 130.4, 130.3, 130.2 (q, J = 31.7 Hz), 129.2 (q, J= 31.7 Hz), 128.8, 127.6, 126.3, 125.2 (q, J = 3.0 Hz), 124.2 (q, J = 271.8Hz), 1.3. 19 F NMR (565 MHz, CDCl3) δ -62.5. HRMS (ESI) (m / z): Calcd forC 27 H 25 F6Si [M+H] + : 491.1630, found: 491.1623. This proves that the yellow oily liquid product obtained from the above reaction is (E)-(4-phenyl-1,1-bis(4-(trifluoromethyl)phenyl)but-1,3-dien-2-yl)trimethylsilane.

[0114] Example 15: Preparation of (E)-(1,1-bis(4-(tert-butyl)phenyl)-4-phenylbut-1,3-dien-2-yl)trimethylsilane

[0115]

[0116] The target product 4o was prepared using 1l, 2h, and 3e as starting substrates, following the same preparation method as in Example 8. It was a yellow oily liquid with a product yield of 63%.

[0117] By nuclear magnetic resonance hydrogen spectrum ( 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 The chemical shift and fragmentation of the yellow oily liquid product were analyzed by C NMR, and the molecular weight was determined by high-resolution mass spectrometry (HRMS). 1 H NMR (600 MHz, CDCl3)δ 7.29 (d, J = 8.4 Hz, 2H), 7.26 (d, J = 8.4 Hz, 2H), 7.24-7.21 (m, 2H), 7.20-7.17 (m, 2H), 7.15-7.12 (m, 1H), 7.13-7.08 (m, 4H), 7.02 (d, J = 16.6Hz, 1H), 6.45 (d, J = 16.6 Hz, 1H), 1.31 (s, 9H), 1.29 (s, 9H), -0.05 (s,9H). 13 C NMR (151 MHz, CDCl3) δ 155.7, 150.6, 149.7, 142.4, 140.8, 138.7,138.6, 133.8, 130.4, 129.9, 129.7, 128.6, 126.8, 126.2, 124.8, 124.7, 34.7,34.6, 31.6, 31.5, 1.6. HRMS (ESI) (m / z): Calcd for C 33 H 42 NaSi [M+Na] + :489.2953, found: 489.2944. This proves that the yellow oily liquid product obtained from the above reaction is (E)-(1,1-bis(4-(tert-butyl)phenyl)-4-phenylbut-1,3-dien-2-yl)trimethylsilane.

[0118] Example 16: Preparation of (E)-(4-(4-methoxyphenyl)-1,1-diphenylbut-1,3-dien-2-yl)trimethylsilane

[0119]

[0120] 1a, 2a, and 3f were used as starting substrates to prepare the target product 4p, using the same method as in Example 8. The product was a yellow solid with a yield of 68%.

[0121] By nuclear magnetic resonance hydrogen spectrum ( 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 The chemical shift and splitting of the yellow solid product were analyzed by C NMR, and the molecular weight was determined by high-resolution mass spectrometry (HRMS). 1 H NMR (600 MHz, CDCl3) δ7.36 -7.27 (m, 5H), 7.26-7.20 (m, 5H), 7.17 (d, J = 8.7 Hz, 1H), 6.93 (d, J =16.6 Hz, 1H), 6.83 (d, J = 8.7 Hz, 1H), 6.46 (d, J = 16.6 Hz, 1H), 3.81 (s, 3H), 0.03 (s, 9H). 13 C NMR (151 MHz, CDCl3) δ 158.9, 154.7, 145.3, 143.9,139.3, 131.3, 130.6, 130.2, 130.1, 128.0, 128.0, 127.5, 127.3, 126.9, 114.1,55.4, 1.6. HRMS (ESI) (m / z): Calcd for C 26 H 29 OSi [M+H] + : 385.1988, found:385.1979. This proves that the yellow solid product obtained from the above reaction is (E)-(4-(4-methoxyphenyl)-1,1-diphenylbut-1,3-dien-2-yl)trimethylsilane.

[0122] Example 17: Preparation of (E)-(1,1-diphenyl-4-(p-tolyl)but-1,3-dien-2-yl)trimethylsilane

[0123]

[0124] 1a, 2a, and 3g were used as starting substrates to prepare the target product 4q, using the same method as in Example 8. The product was a white solid with a yield of 53%.

[0125] By nuclear magnetic resonance hydrogen spectrum ( 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 The chemical shift and splitting of the white solid product were analyzed by C NMR, and the molecular weight was determined by high-resolution mass spectrometry (HRMS). 1H NMR (600 MHz, CDCl3) δ7.36 -7.28 (m, 5H), 7.27-7.21 (m, 5H), 7.17-7.13 (d, J = 8.0 Hz, 2H), 7.10(d, J = 8.0 Hz, 2H), 7.02 (d, J = 16.6 Hz, 1H), 6.49 (d, J = 16.6 Hz, 1H), 2.35 (s, 3H), 0.04 (s, 9H). 13 C NMR (151 MHz, CDCl3) δ 155.0, 145.2, 143.8,139.4, 136.8, 135.7, 132.3, 131.0, 130.2, 130.1, 129.3, 128.0, 128.0, 127.5,126.9, 126.1, 21.3, 1.5. HRMS (ESI) (m / z): Calcd for C 26 H 28 NaSi [M+Na] + :391.1858, found: 391.1854. This proves that the white solid product obtained from the above reaction is (E)-(1,1-diphenyl-4-(p-tolyl)but-1,3-dien-2-yl)trimethylsilane.

[0126] Example 18: Preparation of (E)-(1,1-diphenyl-4-(4-(trifluoromethyl)phenyl)but-1,3-dien-2-yl)trimethylsilane

[0127]

[0128] The target product 4r was prepared using 1a, 2a, and 3h as starting substrates, following essentially the same procedure as in Example 8. The product was a yellow oily liquid with a yield of 64%.

[0129] By nuclear magnetic resonance hydrogen spectrum ( 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 The chemical shift and fragmentation of the yellow oily liquid product were analyzed by C NMR, and the molecular weight was determined by high-resolution mass spectrometry (HRMS). 1H NMR (600 MHz, CDCl3)δ 7.57 (d, J = 8.1 Hz, 2H), 7.42-7.37 (m, 3H), 7.37-7.33 (m, 4H), 7.32-7.28(m, 3H), 7.26 (m, 2H), 7.16 (d, J = 16.5 Hz, 1H), 6.53 (d, J = 16.5 Hz, 1H), 0.10 (s, 9H). 13 C NMR (151 MHz, CDCl3) δ 156.6, 144.9, 143.7, 142.1, 139.3,136.1, 130.1, 130.0, 129.6, 128.9 (q, J = 32.3 Hz), 128.1, 128.1, 127.8,127.2, 126.2, 125.6 (q, J = 4.0 Hz), 124.5 (q, J = 271.8 Hz), 1.4. HRMS (ESI)(m / z): Calcd for C 26 H 26 F3Si [M+H] + : 423.1756, found: 423.1763. This proves that the yellow oily liquid product obtained from the above reaction is (E)-(1,1-diphenyl-4-(4-(trifluoromethyl)phenyl)but-1,3-dien-2-yl)trimethylsilane.

[0130] Example 19: Preparation of (2,2-diphenyl-1-(p-tolyl)vinyl)trimethylsilane

[0131]

[0132] Prepare a clean, dry 10 ml Shrek tube with a suitable magnetic magnet. In a glove box, add 0.016 mmol of nickel(II) ditriphenylphosphine dichloride and 0.2 mmol of potassium fluoride to the Shrek tube. Vacuum the tube three times under a double-row configuration to ensure the side arm is also under nitrogen. Under a nitrogen flow, add 1a (0.2 mmol), 2a (0.6 mmol), 3e (0.6 mmol, 0.6 ml), and ethylene glycol dimethyl ether (1 ml) sequentially to the 10 ml Shrek tube. After addition, stir at 30°C for 24 h. After the reaction is complete and cooled to room temperature, dilute with ethyl acetate. Quench the aluminum reagent with water and 1 mol / L dilute hydrochloric acid. Extract with ethyl acetate and saturated brine. Dry the resulting organic phase and remove the solvent using a rotary evaporator. Separate the residue by column chromatography to obtain a 68% yield of 4 h, a white solid.

[0133] By nuclear magnetic resonance hydrogen spectrum ( 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 The chemical shift and splitting of the white solid product were analyzed by C NMR, and the molecular weight was determined by high-resolution mass spectrometry (HRMS). 1 H NMR (600 MHz, CDCl3) δ7.31 (m, J = 3.4 Hz, 4H), 7.27 (m, 1H), 7.00-6.97 (m, 2H), 6.96-6.90 (m, 5H), 6.84 (m, 2H), 2.22 (s, 3H), -0.22 (s, 9H). 13 C NMR (151 MHz, CDCl3) δ 153.7,144.6, 144.4, 143.6, 140.9, 134.3, 129.6, 129.5, 129.3, 128.3, 128.1, 127.4,127.2, 126.0, 21.2, 0.6. HRMS (ESI) (m / z): Calcd for C 24 H 27 Si [M+H] + 343.1882, found: 343.1882. This proves that the white solid product obtained from the above reaction is (2,2-diphenyl-1-(p-tolyl)vinyl)trimethylsilane.

[0134] Example 20: Preparation of trimethyl(1,2,2-triphenylvinyl)silane

[0135]

[0136] 1a, 2a, and 3j were used as starting substrates to prepare the target product 4t, and the preparation method was basically the same as the operation steps in Example 19. The product was a white solid with a yield of 70%.

[0137] By nuclear magnetic resonance hydrogen spectrum ( 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 The chemical shift and splitting of the white solid product were analyzed by C NMR, and the molecular weight was determined by high-resolution mass spectrometry (HRMS). 1H NMR (600 MHz, CDCl3) δ7.46 -7.38 (m, 4H), 7.35 (m, 1H), 7.20 (m, 2H), 7.14-7.03 (m, 7H), 7.03-6.97(m, 1H), -0.10 (s, 9H). 13 C NMR (151 MHz, CDCl3) δ 154.1, 144.6, 144.6, 144.3,143.6, 129.7, 129.5, 128.1, 127.6, 127.4, 127.3, 126.1, 125.1, 0.6. HRMS(ESI) (m / z): Calcd for C 23 H 25 Si [M+H] + : 329.1726, found: 329.1734. This proves that the white solid product obtained from the above reaction is trimethyl(1,2,2-triphenylvinyl)silane.

[0138] Following the method of Example 19, various substituted trimethyl(1,2,2-triarylvinyl)silanes can be prepared by varying the substituents on the aryl groups of alkynylsilanes, aryl iodides, and aryl aluminum reagents. According to the literature (Zanghui Zhang. Chem. Commun. 2018, 54, 10598-10601.), alkenylsilanes and NBS can be reacted in acetonitrile by heating to convert the alkenylsilanes into alkenyl bromides. According to the literature (Ben ZhongTang. Angew. Chem. Int. Ed. 2025, 64, e202511678.), alkenyl bromides can be coupled with arylboronic acid under palladium catalysis to prepare various tetraphenylethylene molecules. Tetraphenylene is a key building block of aggregation-induced emission materials (Ben Zhong Tang. Chem. Rev. 2015, 115, 21, 11718-11940.).

[0139] The above description is merely a general embodiment of the present invention and is not intended to limit the present invention in any way. Any simple modifications or equivalent changes made to the above embodiments based on the technical essence of the present invention shall fall within the protection scope of the present invention.

Claims

1. A method for nickel-catalyzed synthesis of silicon-containing tetrasubstituted olefin compounds, characterized in that... Includes the following steps: Under nitrogen protection, alkynylsilane, aryl iodide, and organoaluminum reagent were thoroughly mixed in a solvent system in the presence of a nickel catalyst and a bifunctionalization reaction was carried out at 30-40℃ for 12-24 h. After the reaction was completed and cooled to room temperature, ethyl acetate was added for dilution, the aluminum reagent was quenched with water and dilute hydrochloric acid, and the mixture was extracted with ethyl acetate and saturated brine. The resulting organic phase was dried and the solvent was removed by rotary evaporation. The residue was separated by column chromatography or preparative high-performance liquid chromatography to obtain the target product. The organoaluminum reagent is an alkenyl aluminum reagent. or aryl aluminum reagent ; When the organoaluminum reagent is an arylaluminum reagent At that time, the reaction system also included KF; The reaction route is shown below: ； In the formula, substituent Ar is selected from substituted or unsubstituted aryl groups, Ar' is selected from substituted or unsubstituted aryl groups, R is selected from one or more of aryl, alkyl, and hydrogen groups, and R 1 It is selected from substituted or unsubstituted aryl, substituted or unsubstituted alkyl, and cycloalkyl; the substituent used for substitution is selected from one or more of C1-C6 alkyl, C1-C6 alkoxy, halogen, and C1-C6 alkoxycarbonyl.

2. The method according to claim 1, characterized in that: The nickel catalyst is nickel(II) ditriphenylphosphine dichloride.

3. The method according to claim 1, characterized in that: The molar ratio of alkynylsilane, aryl iodide and organoaluminum reagent is controlled to be 1:2~3:2~3.

4. The method according to claim 1, characterized in that: The molar ratio of alkynylsilane and potassium fluoride is controlled at 1:

1.

5. The method according to claim 1, characterized in that: The solvent is dry diethyl ether, or a mixture of dry cyclopentyl methyl ether and dry tert-butyl methyl ether, or a mixture of dry 1,4-dioxane and dry diethyl ether, or a mixture of dry n-hexane and dry ethylene glycol dimethyl ether.

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