A method for preparing alkynylsilanes catalyzed by manganese

Abstract

The present invention discloses a method for preparing alkynylsilanes catalyzed by manganese. The method is as follows: under the protection of an inert gas, a tridentate nitrogen ligand (I), a manganese salt and a reaction solvent are mixed. After stirring and mixing evenly, alkyne (II), an activator and silane (III) are added, and the reaction is carried out at 80-140 °C for 6-14 h. Then, the reaction solution is post-treated to obtain the product alkynylsilane (IV). The present invention uses a manganese salt as a catalyst precursor, and a novel benzimidazole pyridine imine compound as a ligand and a manganese metal precursor as a catalyst to carry out the dehydrogenative silylation coupling reaction of alkynes and silanes in a "one-pot" method. Compared with the existing methods, this method has the advantages of simple operation, mild reaction conditions, wide scope of reaction substrates, high selectivity and high efficiency, and has great practical application value in synthesis.

Description

Technical Field

[0001] The present invention relates to a method for preparing alkynylsilanes catalyzed by manganese, and particularly to a method for preparing alkynylsilanes by using a novel rigid framework tridentate nitrogen ligand and a manganese metal compound as a catalyst. Background Art

[0002] Alkynylsilanes are an important class of organic compounds and important intermediates for constructing C-C bonds and C-X bonds. Therefore, it is of great significance to develop efficient synthetic methods for alkynylsilanes.

[0003] The traditional method for synthesizing alkynylsilanes is the reaction of terminal alkynes with chlorosilanes under the conditions of active metal reagents such as lithium reagents, Grignard reagents, zinc reagents, etc. However, the use of active metal reagents limits the functional group compatibility. Recently, the dehydrogenative coupling reaction of terminal alkynes with silanes has received extensive attention due to its high atom economy. The catalytic systems include transition metal catalysis, inorganic base catalysis, non-metal catalysis, etc. Among them, non-metal catalytic systems such as B(C 6 F 5 ) 3 / organic base, and inorganic base catalytic systems such as NaOH, KOH, etc. have a slow reaction rate and a long reaction time. Transition metals can also be used to catalyze the dehydrogenative coupling of terminal alkynes with silanes, such as noble metals like Au, Pd, Pt, Ru, etc. Recently, catalytic systems of inexpensive metals such as Co, Cu, Zn, etc. have also been reported. However, the Co catalyst has a relatively complex structure and a large limitation in the types of substrates, the Cu system needs to be carried out under light irradiation conditions, and the amount of catalyst used in the Zn catalytic system is as high as 20 mol%. Therefore, there is an urgent need to develop an efficient inexpensive metal catalytic system.

[0004] Recently, we found that the dehydrogenative coupling system of terminal alkynes with silanes catalyzed by Mn has high atom economy, mild conditions and wide substrate adaptability. This efficient method for preparing alkynylsilanes catalyzed by manganese is of great significance. Summary of the Invention

[0005] The object of the present invention is to provide a method for preparing alkynylsilanes catalyzed by a manganese metal, and the catalytic system of this method has high chemoselectivity and regioselectivity, wide substrate compatibility, high efficiency and simple operation.

[0006] The technical solution of the present invention is as follows:

[0007] A method for preparing alkynylsilanes catalyzed by manganese, the method is:

[0008] Under the protection of inert gas, a tridentate nitrogen ligand (I), a manganese salt and a reaction solvent are mixed. After stirring and mixing evenly, an alkyne (II), an activator and a silane (III) are added. The reaction is carried out at 80-140 °C (preferably 120 °C) for 6-14 h (preferably 10 h). After that, the reaction solution is post-treated to obtain the product alkynylsilane (IV);

[0009]

[0010] In formula (II), (III) or (IV),

[0011] R 4 is C1-C30 alkyl, C3-C7 cycloalkyl, halogenated C1-C4 alkyl, trimethylsilyl, naphthyl, heteroaryl, phenyl or substituted phenyl. The benzene ring of the substituted phenyl is substituted by one or more substituents, and the substituents are each independently C1-C30 alkyl, C1-C30 alkoxy, phenyl, hydroxymethyl, halogen, halomethyl or amino;

[0012] R 5 and R 6 are each independently H, C1-C30 alkyl, phenyl or substituted phenyl.

[0013] In the above method, the molar ratio of the alkyne (II) to the silane (III), the activator, the tridentate nitrogen ligand (I) and the manganese salt is 1:1-3:0.1-0.5:0.05-0.1:0.05-0.1, preferably 1:1:0.2:0.05:0.05;

[0014] The reaction solvent includes but is not limited to one or a mixture of two or more of toluene, tetrahydrofuran, anisole, cyclopentyl methyl ether, 1,4-dioxane, n-heptane, dimethyl ether, for example: a mixed solvent of toluene and tetrahydrofuran, a mixed solvent of toluene and dimethyl ether; preferably tetrahydrofuran is used as the reaction solvent; the volume molar ratio of the reaction solvent to the alkyne (II) is 0.5-2:1, mL / mmol, preferably 2:1, mL / mmol;

[0015] The post-treatment method is: after the reaction is completed, when the reaction solution is cooled to room temperature (25 °C), it is quenched and diluted with dichloromethane, concentrated and then separated by silica gel (200-300 mesh) column chromatography. Petroleum ether is used as the eluent, and the eluent containing the target compound is collected, the solvent is evaporated and dried to obtain the product alkynylsilane (IV).

[0016] In the present invention, the structural formula of the manganese salt is MnX 2 , X is halogen, OAc, OTf or acac; preferably the manganese salt is MnCl 2 .

[0017] In the present invention, the structural formula of the activator is: R 7OM or MOH; R 7 is a C1-C6 alkyl group, preferably a tert-butyl group; M is Li, Na or K, preferably K; particularly preferably, the activator is potassium tert-butoxide.

[0018] In the present invention, the structural formula of the tridentate nitrogen ligand (I) is as follows:

[0019]

[0020] In formula (I),

[0021] n = 0-2;

[0022] R 1 is a C1-C30 alkyl group, a C3-C7 cycloalkyl group, a naphthyl group, a heteroaryl group, a phenyl group or a substituted phenyl group, the benzene ring of the substituted phenyl group is substituted by one or more substituents, and the substituents are each independently a C1-C30 alkyl group, a C1-C30 alkoxy group, a phenyl group, a hydroxymethyl group, a halogen or a halomethyl group;

[0023] R 2 、R 3 are each independently H, a C1-C30 alkyl group, a C6-C30 aryl group, or a C1-C30 alkyl group or a C6-C30 aryl group containing one or more heteroatoms selected from O, S or N;

[0024] Or, R 2 、R 3 and the group between them together form a benzene ring or a substituted benzene ring, the substituted benzene ring is substituted by one or more substituents, and the substituents are each independently a C1-C30 alkyl group, a C1-C30 alkoxy group, a phenyl group, a hydroxymethyl group, a halogen or a halomethyl group.

[0025] Particularly preferably, the structural formula of the tridentate nitrogen ligand is as shown in formula (I-a):

[0026]

[0027] The tridentate nitrogen ligand (I-a) can be prepared by the following method:

[0028] Mix compound (I-b), compound (I-c), p-TsOH and toluene evenly, and react at 130 °C for 5 h under a N 2 atmosphere. After that, the reaction solution is post-treated to obtain the tridentate nitrogen ligand (I-a);

[0029] Among them, the molar ratio of compound (I-b), compound (I-c), and p-TsOH is 1:1.5-2:1-1.5, preferably 1:1.5:1;

[0030] The post-treatment method is as follows: after the reaction is completed, the reaction solution is centrifuged and the lower-layer solid is washed with toluene. Then the lower-layer solid is added to saturated NaHCO 3 aqueous solution and DCM is added for extraction. The organic phase is concentrated to dryness, slurried with PE and then filtered. The filter cake is dried to obtain the tridentate nitrogen ligand (I-a);

[0031]

[0032] The beneficial effects of the present invention are as follows:

[0033] The present invention uses a manganese salt as a catalyst precursor, and a novel benzimidazole pyridine imine compound as a ligand and a manganese metal precursor as a catalyst to carry out the dehydrogenative silylation coupling reaction of alkynes and silanes by a "one-pot method". Compared with the existing methods, this method has simple operation, mild reaction conditions, a wide range of applicable reaction substrates, high selectivity, high efficiency, and great practical application value in synthesis. Specific embodiments

[0034] The present invention will be further described below through specific examples, but the protection scope of the present invention is not limited thereto.

[0035] The structural formula of the tridentate nitrogen ligand (I-a) used in the following examples is:

[0036]

[0037] The preparation method is as follows:

[0038] Compound I-b (106 mg, 0.4 mmol), compound I-c (90 mg, 0.6 mmol), p-TsOH·H 2 O (84 g, 0.44 mmol) are mixed evenly with 5 mL of toluene. Under N 2 atmosphere, the reaction is carried out at 130 °C for 5 h. After the reaction is completed, the reaction solution is centrifuged and the lower-layer solid is washed with 10 mL of toluene. Then the lower-layer solid is added to 20 mL of saturated NaHCO 3 aqueous solution and 10 mL of DCM is added for extraction. The extraction operation is repeated 3 times. The organic phases are mixed and concentrated to dryness. The residue is slurried with 30 mL of PE and then filtered. The filter cake is the tridentate nitrogen ligand (I-a).

[0039] Example 1: Reaction of phenylacetylene and diphenylsilane:

[0040] (The raw materials are )

[0041] Under an inert atmosphere, 9.9 mg (5 mol%) of the tridentate nitrogen ligand (I-a) and MnCl 2(3.2 mg, 5 mol%) and tetrahydrofuran (0.5 mL). After stirring for 20 min, base t-BuOK (12.0 mg, 20 mol%), starting material phenylacetylene (55 μL), reactant diphenylsilane (140 μL, 1 eq.) and tetrahydrofuran (0.5 mL) were added and the resulting mixture was stirred evenly. The reaction was carried out in an oil bath at 120 °C for 10 h. After the reaction was completed, the reaction system was cooled to room temperature, diluted and quenched with 3 mL of DCM, concentrated, and the NMR yield was 80%. The product characterization data are as follows: 1 H NMR (500 MHz, CDCl 3 ) δ 7.74 (d, J = 7.9 Hz, 4H), 7.57 (d, J = 8.1 Hz, 4H), 7.48–7.40 (m, 6H), 7.38 - 7.32 (m, 3H), 5.32 (s, 1H).

[0042] Example 2: Reaction of 4-methylphenylacetylene with diphenylsilane:

[0043] (The starting material is )

[0044] Under an inert atmosphere, tridentate nitrogen ligand (I-a) (9.9 mg, 5 mol%), MnCl 2 (3.2 mg, 5 mol%) and tetrahydrofuran (0.5 mL) were successively added to the reaction tube. After stirring for 20 min, base t-BuOK (12.0 mg, 20 mol%), starting material 4-methylphenylacetylene (64 μL), reactant diphenylsilane (140 μL, 1 eq.) and tetrahydrofuran (0.5 mL) were added and the resulting mixture was stirred evenly. The reaction was carried out in an oil bath at 120 °C for 10 h. After the reaction was completed, the reaction system was cooled to room temperature, diluted and quenched with 3 mL of DCM, concentrated, and 108.8 mg of a colorless liquid, the target product, was obtained by flash silica gel column chromatography, with a yield of 73%. The product characterization data are as follows: 1 H NMR (400 MHz, DMSO) δ 7.68 (d, J = 7.8 Hz, 4H), 7.52–7.43 (m, 8H), 7.23 (d, J = 7.9 Hz, 2H), 5.22 (s, 1H), 2.32 (s, 3H).

[0045] Example 3: Reaction of 3-methylphenylacetylene with diphenylsilane:

[0046] (The starting material is )

[0047] Under an inert atmosphere, tridentate nitrogen ligand (I-a) (9.9 mg, 5 mol%), MnCl 2(3.2 mg, 5 mol%) and tetrahydrofuran (0.5 mL). After stirring for 20 min, base t-BuOK (12.0 mg, 20 mol%), starting material 3-methylphenylacetylene (64 μL), reactant diphenylsilane (140 μL, 1 eq.) and tetrahydrofuran (0.5 mL) were added, and the resulting mixture was stirred evenly. The reaction was carried out in an oil bath at 120 °C for 10 h. After the reaction was completed, the reaction system was cooled to room temperature, diluted and quenched with 3 mL of DCM, concentrated, and the crude product was quickly purified by silica gel column chromatography to obtain 101.7 mg of a colorless liquid, which was the target product, yield: 68%. The product characterization data are as follows: 1 H NMR (400 MHz, CDCl 3 ) δ 7.79 (d, J = 7.7 Hz, 4H), 7.53 - 7.39 (m, 8H), 7.31 - 7.21 (m, 2H), 5.36 (s, 1H), 2.39 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 138.0, 135.3, 132.8, 132.3, 130.2, 130.1, 129.3, 128.3, 128.2, 122.3, 109.9, 86.7, 21.2.

[0048] Example 4: Reaction of 2-methylphenylacetylene with diphenylsilane:

[0049] (The starting material is )

[0050] Under an inert atmosphere, tridentate nitrogen ligand (I-a) (9.9 mg, 5 mol%), MnCl 2 (3.2 mg, 5 mol%) and tetrahydrofuran (0.5 mL) were successively added to the reaction tube. After stirring for 20 min, base t-BuOK (12.0 mg, 20 mol%), starting material 2-methylphenylacetylene (64 μL), reactant diphenylsilane (140 μL, 1 eq.) and tetrahydrofuran (0.5 mL) were added, and the resulting mixture was stirred evenly. The reaction was carried out in an oil bath at 120 °C for 10 h. After the reaction was completed, the reaction system was cooled to room temperature, diluted and quenched with 3 mL of DCM, concentrated, and the crude product was quickly purified by silica gel column chromatography to obtain 98.7 mg of a colorless liquid, which was the target product, yield: 66%. The product characterization data are as follows: 1 H NMR (400 MHz, CDCl 3 ) δ 7.81 (d, J = 7.5 Hz, 4H), 7.60 (d, J = 7.6 Hz, 1H), 7.55 - 7.42 (m, 6H), 7.36 - 7.28 (m, 2H), 7.25 - 7.18 (m, 1H), 5.41 (s, 1H), 2.57 (s, 3H).13 C NMR (100 MHz, CDCl 3 ) δ 141.1, 135.3, 132.6, 132.4, 130.2, 129.6, 129.2, 128.2, 125.6, 122.4, 108.6, 91.0, 20.9.

[0051] Example 5: Reaction of 4-tert-butylphenylacetylene with diphenylsilane:

[0052] (The raw materials are )

[0053] Under an inert atmosphere, in a reaction tube, tridentate nitrogen ligand (I-a) (9.9 mg, 5 mol%), MnCl 2 (3.2 mg, 5 mol%) and tetrahydrofuran (0.5 mL) were added in sequence. After stirring for 20 min, base t-BuOK (12.0 mg, 20 mol%), raw material 4-tert-butylphenylacetylene (90 μL), reactant diphenylsilane (140 μL, 1 eq.) and tetrahydrofuran (0.5 mL) were added, and the resulting mixture was stirred evenly. The reaction was carried out in an oil bath at 120 °C for 10 h. After the reaction was completed, the reaction system was cooled to room temperature, diluted and quenched with 3 mL of DCM, concentrated, and the crude product was quickly chromatographed on a silica gel column to obtain 120.7 mg of a colorless liquid, which was the target product, yield: 71%. The product characterization data are as follows: 1 H NMR (400 MHz, CDCl 3 ) δ 7.76 (d, J = 7.8 Hz, 4H), 7.53 (d, J = 8.5 Hz, 2H), 7.50–7.40 (m, 6H), 7.39 (d, J = 8.5 Hz, 2H), 5.34 (s, 1H), 1.37 (s, 9H). 13 C NMR (100 MHz, CDCl 3 ) δ 152.6, 135.3, 132.4, 132.0, 130.1, 128.2, 125.4, 119.5, 109.9, 86.4, 34.9, 31.2.

[0054] Example 6: Reaction of 3,5-dimethoxyphenylacetylene with diphenylsilane:

[0055] (The raw materials are )

[0056] Under an inert atmosphere, in a reaction tube, tridentate nitrogen ligand (I-a) (9.9 mg, 5 mol%), MnCl 2(3.2 mg, 5 mol%) and tetrahydrofuran (0.5 mL). After stirring for 20 min, base t-BuOK (12.0 mg, 20 mol%), starting material 3,5-dimethoxyphenylacetylene (81 mg), reactant diphenylsilane (140 μL, 1 eq.), and tetrahydrofuran (0.5 mL) were added, and the resulting mixture was stirred evenly. The reaction was carried out in an oil bath at 120 °C for 10 h. After the reaction was completed, the reaction system was cooled to room temperature, diluted and quenched with 3 mL of DCM, concentrated, and the crude product was subjected to flash silica gel column chromatography to obtain 120.4 mg of a colorless liquid, which was the target product, with a yield of 70%. The product characterization data is as follows: 1 1H NMR (500 MHz, CDCl 3 ) δ 7.70 (d, J = 7.8 Hz, 2H), 7.50–7.45 (m, 8H), 6.79 (s, 2H), 6.71 (s, 1H), 5.39 (s, 1H), 3.83 (s, 6H).

[0057] Example 7: Reaction of 3-chlorophenylacetylene with diphenylsilane:

[0058] (The starting material is

[0059] Under an inert atmosphere, tridentate nitrogen ligand (I-a) (9.9 mg, 5 mol%), MnCl 2 (3.2 mg, 5 mol%) and tetrahydrofuran (0.5 mL) were successively added to the reaction tube. After stirring for 20 min, base t-BuOK (12.0 mg, 20 mol%), starting material 3-chlorophenylacetylene (68 mg), reactant diphenylsilane (140 μL, 1 eq.), and tetrahydrofuran (0.5 mL) were added, and the resulting mixture was stirred evenly. The reaction was carried out in an oil bath at 120 °C for 10 h. After the reaction was completed, the reaction system was cooled to room temperature, diluted and quenched with 3 mL of DCM, concentrated, and the crude product was subjected to flash silica gel column chromatography to obtain 108.1 mg of a white solid, which was the target product, with a yield of 68%. The product characterization data is as follows: 1 1H NMR (400 MHz, CDCl 3 ) δ 7.77 (d, J = 7.7 Hz, 4H), 7.60 (s, 1H), 7.55–7.42 (m, 7H), 7.41–7.36 (m, 1H), 7.34–7.26 (m, 1H), 5.36 (s, 1H). 13 13C NMR (100 MHz, CDCl 3 ) δ 135.3, 134.2, 132.1, 131.8, 130.4, 130.3, 129.6, 129.5, 128.3, 124.2, 107.7, 88.9.

[0060] Example 8: Reaction of 4-fluorophenylacetylene with diphenylsilane:

[0061] (The raw materials are )

[0062] Under an inert atmosphere, the tridentate nitrogen ligand (I-a) (9.9 mg, 5 mol%), MnCl 2 (3.2 mg, 5 mol%) and tetrahydrofuran (0.5 mL) were successively added to the reaction tube. After stirring for 20 min, the base t-BuOK (12.0 mg, 20 mol%), the raw material 4-fluorophenylacetylene (57 μL), the reactant diphenylsilane (140 μL, 1 eq.) and tetrahydrofuran (0.5 mL) were added, and the resulting mixture was stirred evenly. The reaction was carried out in an oil bath at 120 °C for 10 h. After the reaction was completed, the reaction system was cooled to room temperature, diluted and quenched with 3 mL of DCM, concentrated, and the crude product was quickly chromatographed on a silica gel column to obtain 105.7 mg of a colorless liquid, which was the target product, and the yield was 70%. The product characterization data are as follows: 1 H NMR (400 MHz, CDCl 3 ) δ 7.76 (d, J = 7.7 Hz, 4H), 7.62–7.53 (m, 2H), 7.51–7.40 (m, 6H), 7.10–7.02 (m, 2H), 5.34 (s, 1H). 13 C NMR (100 MHz, CDCl 3 ) δ 164.3 (d, J = 251.1 Hz), 135.3, 134.3 (d, J = 8.5 Hz), 132.1, 130.3, 128.2, 118.7 (d, J = 3.6 Hz), 115.7 (d, J = 22.4 Hz), 108.4, 87.1.

[0063] Example 9: Reaction of 3-fluorophenylacetylene with diphenylsilane:

[0064] (The raw materials are )

[0065] Under an inert atmosphere, the tridentate nitrogen ligand (I-a) (9.9 mg, 5 mol%), MnCl 2(3.2 mg, 5 mol%) and tetrahydrofuran (0.5 mL). After stirring for 20 min, base t-BuOK (12.0 mg, 20 mol%), starting material 3-fluorophenylacetylene (57 μL), reactant diphenylsilane (140 μL, 1 eq.) and tetrahydrofuran (0.5 mL) were added and the resulting mixture was stirred evenly. The reaction was carried out in an oil bath at 120 °C for 10 h. After the reaction was completed, the reaction system was cooled to room temperature, diluted and quenched with 3 mL of DCM, concentrated, and the crude product was subjected to flash silica gel column chromatography to obtain 98.2 mg of a colorless liquid, which was the target product, yield: 65%. The product characterization data are as follows: 1 H NMR (400 MHz, CDCl 3 ) δ 7.79 (d, J = 7.1 Hz, 4H), 7.52–7.44 (m, 6H), 7.42–7.28 (m, 3H), 7.18–7.06 (m, 1H), 5.39 (s, 1H). 13 C NMR (100 MHz, CDCl 3 ) δ 162.3 (d, J = 246.9 Hz), 135.9, 131.9, 130.4, 130.1 (d, J = 8.7 Hz), 128.3, 128.2, 124.4 (d, J = 9.4 Hz), 119.1 (d, J = 22.9 Hz), 116.7 (d, J = 21.3 Hz), 108.0 (d, J = 3.1 Hz), 88.6.

[0066] Example 10: Reaction of 2-fluorophenylacetylene with diphenylsilane:

[0067] (The starting material is )

[0068] Under an inert atmosphere, tridentate nitrogen ligand (I-a) (9.9 mg, 5 mol%), MnCl 2 (3.2 mg, 5 mol%) and tetrahydrofuran (0.5 mL) were successively added to the reaction tube. After stirring for 20 min, base t-BuOK (12.0 mg, 20 mol%), starting material 2-fluorophenylacetylene (57 μL), reactant diphenylsilane (140 μL, 1 eq.) and tetrahydrofuran (0.5 mL) were added and the resulting mixture was stirred evenly. The reaction was carried out in an oil bath at 120 °C for 10 h. After the reaction was completed, the reaction system was cooled to room temperature, diluted and quenched with 3 mL of DCM, concentrated, and the crude product was subjected to flash silica gel column chromatography to obtain 90.6 mg of a colorless liquid, which was the target product, yield: 60%. The product characterization data are as follows: 1 H NMR (400 MHz, CDCl 3) δ 7.77 (d, J = 7.7 Hz, 4H), 7.60–7.52 (m, 1H), 7.51–7.40 (m, 6H), 7.40–7.32 (m, 1H), 7.18–7.06 (m, 2H), 5.36 (s, 1H). 13 C NMR (100 MHz, CDCl 3 ) δ 163.4 (d, J = 253.3 Hz), 135.3, 134.1, 131.9, 131.0 (d, J = 8.0 Hz), 130.3, 128.2, 124.0 (d, J = 3.7 Hz), 115.7 (d, J = 20.8 Hz), 111.3 (d, J = 15.5 Hz), 102.5, 93.1 (d, J = 3.3 Hz).

[0069] Example 11: Reaction of 3-bromophenylacetylene with diphenylsilane:

[0070] (The raw materials are )

[0071] Under an inert atmosphere, a tridentate nitrogen ligand (I-a) (9.9 mg, 5 mol%), MnCl 2 (3.2 mg, 5 mol%) and tetrahydrofuran (0.5 mL) were successively added to a reaction tube. After stirring for 20 min, base t-BuOK (12.0 mg, 20 mol%), raw material 3-bromophenylacetylene (91 mg), reactant diphenylsilane (140 μL, 1 eq.) and tetrahydrofuran (0.5 mL) were added, and the resulting mixture was stirred evenly. The reaction was carried out in an oil bath at 120 °C for 10 h. After the reaction was completed, the reaction system was cooled to room temperature, diluted and quenched with 3 mL of DCM, concentrated, and the crude product was rapidly purified by silica gel column chromatography to obtain 118.0 mg of a colorless liquid, which was the target product, with a yield of 65%. The product characterization data are as follows: 1 H NMR (500 MHz, CDCl 3 ) δ 7.78–7.72 (m, 4H), 7.64–7.61 (m, 1H), 7.54–7.35 (m, 8H), 7.24–7.19 (m, 1H), 5.34 (s, 1H). 13 C NMR (125 MHz, CDCl 3 ) δ 135.3, 134.9, 132.4, 131.8, 130.8, 130.3, 129.8, 128.3, 124.5, 122.2, 107.6, 89.1.

[0072] Example 12: Reaction of 4-bromophenylacetylene with diphenylsilane:

[0073] (The raw material is )

[0074] Under an inert atmosphere, 9.9 mg (5 mol%) of the tridentate nitrogen ligand (I-a), MnCl 2 (3.2 mg, 5 mol%) and 0.5 mL of tetrahydrofuran were successively added to the reaction tube. After stirring for 20 min, 12.0 mg (20 mol%) of the base t-BuOK, 91 mg of the raw material 4-bromophenylacetylene, 140 μL (1 eq.) of the reactant diphenylsilane and 0.5 mL of tetrahydrofuran were added, and the resulting mixture was stirred evenly. The reaction was carried out in an oil bath at 120 °C for 10 h. After the reaction was completed, the reaction system was cooled to room temperature, diluted and quenched with 3 mL of DCM, concentrated, and the crude product was subjected to flash silica gel column chromatography to obtain 118.0 mg of a colorless liquid as the target product, with a yield of 65%. The product characterization data are as follows: 1 H NMR (400 MHz, CDCl 3 ) δ 7.75 (d, J = 6.8 Hz, 4H), 7.53–7.38 (m, 10H), 5.33 (s, 1H). 13 C NMR (100 MHz, CDCl 3 ) δ 135.3, 133.7, 131.9, 131.7, 130.3, 128.3, 123.6, 121.5, 108.3, 88.8.

[0075] Example 13: Reaction of 4-ethynyl-N,N-dimethylaniline with diphenylsilane:

[0076] (The raw material is )

[0077] Under an inert atmosphere, 9.9 mg (5 mol%) of the tridentate nitrogen ligand (I-a), MnCl 2 (3.2 mg, 5 mol%) and 0.5 mL of tetrahydrofuran were successively added to the reaction tube. After stirring for 20 min, 12.0 mg (20 mol%) of the base t-BuOK, 73 mg of the raw material 4-ethynyl-N,N-dimethylaniline, 140 μL (1 eq.) of the reactant diphenylsilane and 0.5 mL of tetrahydrofuran were added, and the resulting mixture was stirred evenly. The reaction was carried out in an oil bath at 120 °C for 10 h. After the reaction was completed, the reaction system was cooled to room temperature, diluted and quenched with 3 mL of DCM, concentrated, and the crude product was subjected to flash silica gel column chromatography to obtain 130.8 mg of a white solid as the target product, with a yield of 80%. The product characterization data are as follows: 1 H NMR (500 MHz, CDCl 3)δ 7.80 (d, J = 7.7 Hz, 4H), 7.56–7.37 (m, 8H), 6.66 (d, J = 8.9 Hz, 2H), 5.38 (s, 1H), 3.01 (s, 6H). 13 C NMR(125 MHz, CDCl 3 )δ 155.4, 140.1, 138.3, 137.8, 134.8, 132.9, 116.4, 113.9, 89.0, 44.9.

[0078] Example 14: Reaction of n-hexyne with diphenylsilane:

[0079] (The raw materials are )

[0080] Under an inert atmosphere, in a reaction tube, tridentate nitrogen ligand (I-a) (9.9 mg, 5 mol%), MnCl 2 (3.2 mg, 5 mol%) and tetrahydrofuran (0.5 mL) were successively added. After stirring for 20 min, base t-BuOK (12.0 mg, 20 mol%), raw material n-hexyne (57 μL), reactant diphenylsilane (140 μL, 1 eq.) and tetrahydrofuran (0.5 mL) were added, and the resulting mixture was stirred evenly. The reaction was carried out in an oil bath at 120 °C for 10 h. After the reaction was completed, the reaction system was cooled to room temperature, diluted and quenched with 3 mL of DCM, concentrated, and the crude product was quickly chromatographed on a silica gel column to obtain 79.2 mg of a colorless liquid, which was the target product, yield: 68%. The product characterization data is as follows: 1 H NMR(500 MHz, CDCl 3 )δ 7.73 (d, J = 7.8 Hz, 4H), 7.48–7.40 (m, 6H), 5.22 (s, 1H), 2.41 (t, J = 7.1 Hz, 2H), 1.69–1.60 (m, 2H), 1.58–1.48 (m, 2H), 1.00 (t, J = 7.3 Hz, 3H). 13 C NMR(125 MHz, CDCl 3 )δ 135.2, 132.9, 123.0, 128.1, 112.9, 77.5, 30.6, 22.0, 19.9, 13.6.

[0081] Example 15: Reaction of trimethylsilylacetylene with diphenylsilane:

[0082] (The raw materials are )

[0083] Under an inert atmosphere, the tridentate nitrogen ligand (I-a) (9.9 mg, 5 mol%) and MnCl 2 (3.2 mg, 5 mol%) and tetrahydrofuran (0.5 mL) were successively added to the reaction tube. After stirring for 20 min, base t-BuOK (12.0 mg, 20 mol%), starting material trimethylsilylacetylene (71 μL), reactant diphenylsilane (140 μL, 1 eq.), and tetrahydrofuran (0.5 mL) were added, and the resulting mixture was stirred evenly. The reaction was carried out in an oil bath at 120 °C for 10 h. After the reaction was completed, the reaction system was cooled to room temperature, diluted and quenched with 3 mL of DCM, concentrated, and the crude product was subjected to flash silica gel column chromatography to obtain 84.0 mg of a colorless liquid, which was the target product, with a yield of 60%. The product characterization data are as follows: 1 H NMR (500 MHz, CDCl 3 ) δ 7.72 (d, J = 7.9 Hz, 4H), 7.49–7.41 (m, 6H), 5.21 (s, 1H), 0.30 (s, 9H). 13 C NMR (125 MHz, CDCl 3 ) δ 135.2, 132.1, 130.1, 128.1, 119.9, 106.1, -0.2.

[0084] Example 16: Reaction of 3-ethynylthiophene with diphenylsilane:

[0085] (The starting material is )

[0086] Under an inert atmosphere, the tridentate nitrogen ligand (I-a) (9.9 mg, 5 mol%) and MnCl 2 (3.2 mg, 5 mol%) and tetrahydrofuran (0.5 mL) were successively added to the reaction tube. After stirring for 20 min, base t-BuOK (12.0 mg, 20 mol%), starting material 3-ethynylthiophene (49 μL), reactant diphenylsilane (140 μL, 1 eq.), and tetrahydrofuran (0.5 mL) were added, and the resulting mixture was stirred evenly. The reaction was carried out in an oil bath at 120 °C for 10 h. After the reaction was completed, the reaction system was cooled to room temperature, diluted and quenched with 3 mL of DCM, concentrated, and the crude product was subjected to flash silica gel column chromatography to obtain 91.2 mg of a colorless liquid, which was the target product, with a yield of 63%. The product characterization data are as follows: 1 H NMR (400 MHz, CDCl 3 ) δ 7.75 (d, J = 7.8 Hz, 4H), 7.62 (d, J = 3.0 Hz, 1H), 7.51–7.38 (m, 6H), 7.31–7.27 (m, 1H), 7.25–7.20 (m, 1H), 5.33 (s, 1H). 1313C NMR (100 MHz, CDCl 3 ) δ 135.3, 132.1, 130.8, 130.2, 130.1, 128.2, 125.5, 121.8, 104.4, 87.0.

[0087] Example 17: Reaction of 5-chloro-1-pentyne with diphenylsilane:

[0088] (The raw materials are )

[0089] Under an inert atmosphere, in a reaction tube, a tridentate nitrogen ligand (I-a) (9.9 mg, 5 mol%), MnCl 2 (3.2 mg, 5 mol%) and tetrahydrofuran (0.5 mL) were added in sequence. After stirring for 20 min, base t-BuOK (12.0 mg, 20 mol%), raw material 5-chloro-1-pentyne (53 μL), reactant diphenylsilane (140 μL, 1 eq.) and tetrahydrofuran (0.5 mL) were added, and the resulting mixture was stirred evenly. The reaction was carried out in an oil bath at 120 °C for 10 h. After the reaction was completed, the reaction system was cooled to room temperature, diluted and quenched with 3 mL of DCM, concentrated, and the crude product was quickly purified by silica gel column chromatography to obtain 71.0 mg of a colorless liquid, which is the target product, yield: 50%. The characterization data of the product are as follows: 1 1H NMR (500 MHz, CDCl 3 ) δ 7.69 (d, J = 7.9 Hz, 4H), 7.48–7.39 (m, 6H), 5.19 (s, 1H), 3.71 (t, J = 6.3 Hz, 2H), 2.58 (t, J = 6.9 Hz, 2H), 2.10–2.03 (m, 2H). 13 13C NMR (125 MHz, CDCl 3 ) δ 135.1, 132.5, 130.1, 128.1, 110.4, 79.1, 43.6, 31.1, 17.6.

[0090] Example 18: Reaction of phenylacetylene with diethylsilane:

[0091] (The raw materials are )

[0092] Under an inert atmosphere, in a reaction tube, a tridentate nitrogen ligand (I-a) (9.9 mg, 5 mol%), MnCl 2(3.2 mg, 5 mol%) and tetrahydrofuran (0.5 mL). After stirring for 20 min, base t-BuOK (12.0 mg, 20 mol%), starting material phenylacetylene (55 μL), reactant diethylsilane (64 μL, 1 eq.) and tetrahydrofuran (0.5 mL) were added, and the resulting mixture was stirred evenly. The reaction was carried out in an oil bath at 120 °C for 10 h. After the reaction was completed, the reaction system was cooled to room temperature, diluted and quenched with 3 mL of DCM, concentrated, and the crude product was subjected to flash silica gel column chromatography to obtain 37.6 mg of a colorless liquid, which was the target product, yield: 40%. The product characterization data is as follows: 1 H NMR (500 MHz, CDCl 3 ) δ 7.51 - 7.46 (m, 2H), 7.34 - 7.28 (m, 3H), 4.09 (s, 1H), 1.11 (t, J = 8.0 Hz, 6H), 0.77 (q, J = 8.0 Hz, 4H). 13 C NMR (125 MHz, CDCl 3 ) δ 132.0, 128.6, 128.2, 123.0, 107.3, 89.2, 7.9, 3.9.

[0093] Example 19: Reaction of phenylacetylene with phenylsilane:

[0094] (The starting material is )

[0095] Under an inert atmosphere, tridentate nitrogen ligand (I-a) (9.9 mg, 5 mol%), MnCl 2 (3.2 mg, 5 mol%) and tetrahydrofuran (0.5 mL) were successively added to the reaction tube. After stirring for 20 min, base t-BuOK (12.0 mg, 20 mol%), starting material phenylacetylene (55 μL), reactant phenylsilane (62 μL, 1 eq.) and tetrahydrofuran (0.5 mL) were added, and the resulting mixture was stirred evenly. The reaction was carried out in an oil bath at 120 °C for 10 h. After the reaction was completed, the reaction system was cooled to room temperature, diluted and quenched with 3 mL of DCM, concentrated, and detected by GC. The yield of the target product by gas phase internal standard (the internal standard is biphenyl) was 50.0%.

[0096] Comparative Example 1: Reaction of phenylacetylene with diphenylsilane using manganese bromide as the precursor:

[0097] (The starting material is )

[0098] Under an inert atmosphere, tridentate nitrogen ligand (I-a) (9.9 mg, 5 mol%), MnBr 2(5.4 mg, 5 mol%) and tetrahydrofuran (0.5 mL). After stirring for 20 min, base t-BuOK (12.0 mg, 20 mol%), starting material phenylacetylene (55 μL), reactant diphenylsilane (140 μL, 1 eq.) and tetrahydrofuran (0.5 mL) were added, and the resulting mixture was stirred evenly. The reaction was carried out in an oil bath at 120 °C for 10 h. After the reaction, the reaction system was cooled to room temperature, diluted and quenched with 3 mL of DCM, concentrated, and the crude product was quickly purified by silica gel column chromatography to obtain 99.4 mg of a white solid, which was the target product, yield: 70%.

[0099] Comparative Example 2: Reaction of phenylacetylene with diphenylsilane without manganese salt:

[0100] (starting material is )

[0101] Under an inert atmosphere, tridentate nitrogen ligand (I-a) (9.9 mg, 5 mol%) and tetrahydrofuran (0.5 mL) were successively added to the reaction tube. After stirring for 20 min, base t-BuOK (12.0 mg, 20 mol%), starting material phenylacetylene (55 μL), reactant diphenylsilane (140 μL, 1 eq.) and tetrahydrofuran (0.5 mL) were added, and the resulting mixture was stirred evenly. The reaction was carried out in an oil bath at 120 °C for 10 h. After the reaction, the reaction system was cooled to room temperature, diluted and quenched with 3 mL of DCM, concentrated, and no target product was detected by GC.

[0102] Comparative Example 3: Reaction of phenylacetylene with diphenylsilane without ligand:

[0103] (starting material is )

[0104] Under an inert atmosphere, MnCl 2 (3.2 mg, 5 mol%) and tetrahydrofuran (0.5 mL) were successively added to the reaction tube. After stirring for 20 min, base t-BuOK (12.0 mg, 20 mol%), starting material phenylacetylene (55 μL), reactant diphenylsilane (140 μL, 1 eq.) and tetrahydrofuran (0.5 mL) were added, and the resulting mixture was stirred evenly. The reaction was carried out in an oil bath at 120 °C for 10 h. After the reaction, the reaction system was cooled to room temperature, diluted and quenched with 3 mL of DCM, concentrated, and no target product was detected by GC.

[0105] Comparative Example 4: Reaction of phenylacetylene with diphenylsilane using toluene as solvent

[0106] (starting material is )

[0107] Under an inert atmosphere, a tridentate nitrogen ligand (I-a) (9.9 mg, 5 mol%) and MnCl 2 (3.2 mg, 5 mol%) and toluene (0.5 mL) were successively added into a reaction tube. After stirring for 20 min, base t-BuOK (12.0 mg, 20 mol%), starting material phenylacetylene (55 μL), reactant diphenylsilane (140 μL, 1 eq.) and toluene (0.5 mL) were added, and the resulting mixture was stirred evenly. The reaction was carried out in an oil bath at 120 °C for 10 h. After the reaction was completed, the reaction system was cooled to room temperature, diluted and quenched with 3 mL of DCM, concentrated, and the crude product was quickly purified by silica gel column chromatography to obtain 56.8 mg of a white solid, which was the target product, with a yield of 40%.

[0108] Finally, it should also be noted that the above are only several specific embodiments of the present invention. Obviously, the present invention is not limited to the above embodiments and there can be many variations. Any equivalent structural or equivalent process transformation made by using the content of the specification of the present invention, or directly or indirectly applied in other related technical fields, is similarly included in the protection scope of the present invention.

Claims

1. A method for preparing manganese-catalyzed alkynylsilanes, characterized in that, the method is as follows: Under the protection of inert gas, a tridentate nitrogen ligand (I), a manganese salt and a reaction solvent are mixed, and after stirring and mixing evenly, alkyne (II), an activator, and silane (III) are added, and the reaction is carried out at 80-140 °C for 6-14 h. Then, the reaction solution is post-treated to obtain the product alkynylsilane (IV); wherein, The structural formula of the manganese salt is MnX 2 , where X is halogen, OAc, OTf or acac; The structural formula of the activator is: R 7 OM or MOH; R 7 is a C1-C6 alkyl group; M is Li, Na or K; the structural formula of the tridentate nitrogen ligand (I) is as follows: the structural formulas of alkyne (II), silane (III), and the product alkynylsilane (IV) are as follows: In formula (II), (III) or (IV), R 4 is a C1-C30 alkyl group, a C3-C7 cycloalkyl group, a halogenated C1-C4 alkyl group, a trimethylsilyl group, a naphthyl group, a heteroaryl group, a phenyl group or a substituted phenyl group, the benzene ring of the substituted phenyl group is substituted with one or more substituents, and each of the substituents is independently a C1-C30 alkyl group, a C1-C30 alkoxy group, a phenyl group, a hydroxymethyl group, a halogen, a halogenated methyl group or an amino group; R 5 and R 6 are each independently H, a C1-C30 alkyl group or a phenyl group.

2. The method for preparing manganese-catalyzed alkynylsilanes according to claim 1, characterized in that, the molar ratio of alkyne (II) to silane (III), activator, tridentate nitrogen ligand (I), and manganese salt is 1:1-3:0.1-0.5:0.05-0.1:0.05-0.

1.

3. The method for preparing manganese-catalyzed alkynylsilanes according to claim 1, characterized in that, the reaction solvent is one or a mixed solvent of two or more of toluene, tetrahydrofuran, anisole, cyclopentyl methyl ether, 1,4-dioxane, n-heptane, and dimethyl ether in any proportion.

4. The method for preparing manganese-catalyzed alkynylsilanes according to claim 1, characterized in that, the volume molar ratio of the reaction solvent to alkyne (II) is 0.5-2:1, mL / mmol.

5. The method for preparing manganese-catalyzed alkynylsilanes according to claim 1, characterized in that, the post-treatment method is: after the reaction is completed, wait for the reaction solution to cool to room temperature, quench and dilute it with dichloromethane, concentrate it, and then carry out silica gel column chromatography separation. Using petroleum ether as the eluent, collect the eluent containing the target compound, evaporate the solvent and dry it to obtain the product alkynylsilane (IV).

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