阅读说明：本技术 一种烷基硅化合物的合成方法 (Synthesis method of alkyl silicon compound ) 是由 邱晓东 周丽 王浩然 陆玲依 于 2021-10-12 设计创作，主要内容包括：本发明属于有机化学合成领域,公开了一种烷基硅化合物的合成方法。本发明使用二价镍催化剂和氮杂环卡宾配体,在催化量锌粉和磷酸钾的作用,烯基醚化合物、硅硼试剂(Et-(3)Si-BPin)和三乙基硅烷反应实现四级烷基硅化合物的合成。本发明合成方法不仅适用于富电子的芳基乙烯甲醚,而且含有缺电子芳基或杂环结构的原料都能以较高的产率得到烷基硅产物。这为碳-杂键的形成提供了一种新的方式,扩大了惰性C-O键活化的范围。(The invention belongs to the field of organic chemical synthesis, and discloses a synthetic method of an alkyl silicon compound. The invention uses divalent nickel catalyst and N-heterocyclic carbene ligand, and alkenyl ether compound and silicon boron reagent (Et) are used under the action of catalytic amount of zinc powder and potassium phosphate 3 Si-BPin) and triethylsilane to synthesize the quaternary alkyl silicon compound. The synthesis method is not only suitable for electron-rich aryl vinyl methyl ether, but also can obtain alkyl silicon products with higher yield from raw materials containing electron-deficient aryl or heterocyclic structures. This provides a new way for the formation of carbon-heterobonds, extending the range of inert C-O bond activation.)

1. A method for synthesizing an alkyl silicon compound is characterized in thatTaking alkenyl methyl ether 1, a silicon boron reagent 2 and triethylsilane as raw materials, taking nickel acetylacetonate as a catalyst, taking N-heterocyclic carbene IMes & HCl as a ligand, taking zinc powder and potassium phosphate as additives, stirring and reacting for 24 hours in a toluene solvent at 110 ℃ under the protection of nitrogen, decompressing and distilling to remove the solvent after the reaction is finished to obtain a crude product, taking petroleum ether and ethyl acetate as eluent, and separating the crude product by column chromatography to obtain a triethylsilane compound 3; the silicon boron reagent 2 is Et₃Si-BPin；

The reaction formula of the synthesis method is as follows:

wherein, the substituent R in the reaction formula¹，R²，R³Respectively as follows: r¹Is phenyl, R²Hydrogen, R³Hydrogen; r¹4-methylphenyl, R²Hydrogen, R³Hydrogen; r¹(ii) 3-methylphenyl, R²Hydrogen, R³Hydrogen; r¹4-tert-butylphenyl group, R²Hydrogen, R³Hydrogen; r¹4-phenylphenyl, R²Hydrogen, R³Hydrogen; r¹4- (2-pyridyl) phenyl, R²Hydrogen, R³Hydrogen; r¹4-methoxyphenyl radical, R²Hydrogen, R³Hydrogen; r¹3, 5-dimethylphenyl, R²Hydrogen, R³Hydrogen; r¹3, 4-dimethoxyphenyl, R²Hydrogen, R³Hydrogen; r¹3, 5-dimethoxyphenyl, R²Hydrogen, R³Hydrogen; r¹3,4, 5-trimethoxyphenyl, R²Hydrogen, R³Hydrogen; r¹(1-benzodihydrofuran-5-yl), R²Hydrogen, R³Hydrogen; r¹4-fluorophenyl, R²Hydrogen, R³Hydrogen; r¹4-trifluoromethylphenyl group, R²Hydrogen, R³Hydrogen; r¹4-methoxycarbonylphenyl, R²Hydrogen, R³Hydrogen; r¹Is N, N-dimethylbenzamide-4-yl, R²Hydrogen, R³Hydrogen; r¹2-methylphenyl, R²Hydrogen, R³Hydrogen; r¹2-methoxy-4-dimethylaminophenyl radical, R²Hydrogen, R³Hydrogen; r¹2-naphthyl, R²Hydrogen, R³Hydrogen; r¹1-naphthyl, R²Hydrogen, R³Hydrogen; r¹9-anthracenyl, R²Hydrogen, R³Hydrogen; r¹Is phenyl, R²Is phenyl, R³Hydrogen; r¹Is phenyl, R²Hydrogen, R³Methyl group; r¹2-furyl radical, R²Hydrogen, R³Hydrogen; r¹2-benzofuranyl, R²Hydrogen, R³Hydrogen; r¹2-methyl-6-methylpyridin-2-yl, R²Hydrogen, R³Hydrogen; r¹Is N-methylimidazol-2-yl, R²Hydrogen, R³Hydrogen; r¹Is 5-pyrimidinyl radical, R²Hydrogen, R³Hydrogen; r¹(ii) 3-quinolinyl, R²Hydrogen, R³Hydrogen; r¹2-quinolyl, R²Hydrogen, R³Hydrogen; r¹Is N-methylindol-3-yl, R²Hydrogen, R³Hydrogen; r¹Is 4-indolyl, R²Hydrogen, R³Hydrogen; r¹Is 7-indolyl, R²Hydrogen, R³Hydrogen; r¹Is N-methyl-7-azaindol-3-yl, R²Hydrogen, R³Hydrogen; r¹Is N-ethylcarbazol-3-yl, R²Hydrogen, R³Hydrogen.

2. The synthesis method of claim 1, wherein the molar ratio of alkenyl methyl ether 1: silicon boron reagent 2: triethylsilane: nickel acetylacetonate: nitrogen heterocyclic carbene: zinc powder: potassium phosphate is 10:20:30:1:1:2: 15.

Technical Field

The invention belongs to the field of organic chemical synthesis, and particularly relates to a method for synthesizing an alkyl silicon compound, in particular to a method for synthesizing a quaternary alkyl silicon compound by C-O bond fracture silicification and carbon-carbon double bond hydrogenation reduction of an alkenyl methyl ether compound catalyzed by a divalent nickel catalyst.

Background

Olefin-catalyzed hydrosilation is an important method for producing various functional silicon compounds and bioactive silane compounds, (chem.rev.,2016, 116,11654), and some noble metal catalysts such as Pt, Rh, Pd, Ru, etc. have been intensively studied in the field of olefin hydrosilation (RSC adv.,2015,5, 20603), but the application of these synthetic methods is limited due to the high price of the catalysts. Recently, the development of inexpensive transition metal catalysts has made the catalytic hydrosilation reaction more applicable. The Ritter project group achieved 1, 4-hydrosilation addition reactions of conjugated dienes using iron catalysts (j.am. chem. soc.,2010,132,13214). Dungheng et al developed a method for the synthesis of linear alkyl silanes by cobalt-catalyzed hydrosilation of terminal alkenes (angelw.chem.int.ed., 2013,52, 10845). A similar reaction was also reported by the Holland topic group (j.am. chem. soc., 2015,137,13244). The humi group achieved hydrosilation of common polysubstituted olefins, including terminal olefins, using nickel catalysts (angelw. chem. int. ed.,2015,54, 14523). The Huangjing project group realizes selective hydrosilation reaction of terminal olefin by designing and synthesizing a novel iron catalyst and a cobalt catalyst to respectively obtain straight chain alkyl silicon and branched chain alkyl silicon compounds (Angew. chem. int. Ed.,2016,55, 6671). The Fout group achieved a hydrosilation reaction (ACS cat, 2016,6,3589) compatible with a variety of heteroatom-group-terminated olefins via cobalt catalyst design. The byshemine group applied cobalt catalysts to the hydrosilation of allenes to synthesize allylsilane compounds (org. chem. front.,2017,4, 1829). Thomas topic group catalyzed the hydrosilation of terminal olefins with manganese catalysts to synthesize linear alkyl silicon compounds (angelw. chem. int. ed.,2018,57, 10620). The zhu-wairather group realizes the catalytic hydrosilation reaction of simple intermediate olefins by designing a synthetic iron catalyst (nat. Commun.,2018,9, 221). The Huangzheng group improved cobalt catalysts for selective 1, 2-hydrosilation addition reactions of conjugated dienes (ACS Catal.,2019,9, 1612). The catalytic reaction utilizes cheap transition metal catalyst, saves synthesis cost, but is still limited to terminal olefin or simple disubstituted olefin in the aspect of application range of olefin raw material, and has limited compatible functional group, and has low reactivity to olefin containing heteroatom groups such as nitrogen and oxygen and heterocyclic olefin. The method for synthesizing the alkyl silicon by taking the alkenyl methyl ether compound as a raw material and carrying out silicon silylation through a carbon-oxygen bond and reduction of double bonds in series is a novel synthesis method, and is compatible with a series of nitrogen, oxygen and fluorine heteroatom groups and nitrogen and oxygen heterocyclic structure units.

Disclosure of Invention

In view of the above, the present invention is directed to a method of producing a polymer by using Ni (acac)₂A process for the catalytic demethoxyhydrosilation of an alkenyl methyl ether to synthesize triethylsilane. Reaction sourceThe source of the material is wide, the experimental method is simple, convenient and efficient, and the product is easy to separate, thus being beneficial to the research on the activation of the inert C-O bond.

The invention provides a method for synthesizing an alkyl silicon compound, which takes alkenyl methyl ether 1, a silicon boron reagent 2 and triethylsilane as raw materials and acetylacetone nickel Ni (acac)₂Taking N-heterocyclic carbene IMes & HCl as a ligand, taking zinc powder and potassium phosphate as additives, stirring and reacting for 24 hours in a toluene solvent at 110 ℃ under the protection of nitrogen, decompressing and steaming to remove the solvent after the reaction is finished to obtain a crude product, taking petroleum ether and ethyl acetate as eluent, and separating the crude product by column chromatography to obtain a compound 3; wherein the silicon boron reagent 2 is Et₃Si-BPin；

The reaction formula of the synthesis method is as follows:

wherein, the substituent R in the reaction formula¹，R²，R³Respectively as follows: r¹Is phenyl, R²Hydrogen, R³Hydrogen; r¹4-methylphenyl, R²Hydrogen, R³Hydrogen; r¹(ii) 3-methylphenyl, R²Hydrogen, R³Hydrogen; r¹4-tert-butylphenyl group, R²Hydrogen, R³Hydrogen; r¹4-phenylphenyl, R²Hydrogen, R³Hydrogen; r¹4- (2-pyridyl) phenyl, R²Hydrogen, R³Hydrogen; r¹4-methoxyphenyl radical, R²Hydrogen, R³Hydrogen; r¹3, 5-dimethylphenyl, R²Hydrogen, R³Hydrogen; r¹3, 4-dimethoxyphenyl, R²Hydrogen, R³Hydrogen; r¹3, 5-dimethoxyphenyl, R²Hydrogen, R³Hydrogen; r¹3,4, 5-trimethoxyphenyl, R²Hydrogen, R³Hydrogen; r¹(1-benzodihydrofuran-5-yl), R²Hydrogen, R³Hydrogen; r¹4-fluorophenyl, R²Hydrogen, R³Hydrogen; r¹4-trifluoromethylphenyl group, R²Hydrogen, R³Hydrogen; r¹4-methoxycarbonylphenyl, R²Hydrogen, R³Hydrogen; r¹Is N, N-dimethylbenzamide-4-yl, R²Hydrogen, R³Hydrogen; r¹2-methylphenyl, R²Hydrogen, R³Hydrogen; r¹2-methoxy-4-dimethylaminophenyl radical, R²Hydrogen, R³Hydrogen; r¹2-naphthyl, R²Hydrogen, R³Hydrogen; r¹1-naphthyl, R²Hydrogen, R³Hydrogen; r¹9-anthracenyl, R²Hydrogen, R³Hydrogen; r¹Is phenyl, R²Is phenyl, R³Hydrogen; r¹Is phenyl, R²Hydrogen, R³Methyl group; r¹2-furyl radical, R²Hydrogen, R³Hydrogen; r¹2-benzofuranyl, R²Hydrogen, R³Hydrogen; r¹2-methyl-6-methylpyridin-2-yl, R²Hydrogen, R³Hydrogen; r¹Is N-methylimidazol-2-yl, R²Hydrogen, R³Hydrogen; r¹Is 5-pyrimidinyl radical, R²Hydrogen, R³Hydrogen; r¹(ii) 3-quinolinyl, R²Hydrogen, R³Hydrogen; r¹2-quinolyl, R²Hydrogen, R³Hydrogen; r¹Is N-methylindol-3-yl, R²Hydrogen, R³Hydrogen; r¹Is 4-indolyl, R²Hydrogen, R³Hydrogen; r¹Is 7-indolyl, R²Hydrogen, R³Hydrogen; r¹Is N-methyl-7-azaindol-3-yl, R²Hydrogen, R³Hydrogen; r¹Is N-ethylcarbazol-3-yl, R²Hydrogen, R³Hydrogen.

Further, the dosage of the raw materials and the reaction reagents, alkenyl methyl ether 1: silicon boron reagent 2: HSiEt₃：Ni(acac)₂: IMes & HCl: zinc powder: the molar ratio of potassium phosphate is 10:20:30:1:1:2: 15.

the alkenyl methyl ether 1 has the following raw material structure:

sequentially comprises the following steps: styryl methyl ether, p-methylstyrene methyl ether, m-methylstyrene methyl ether, p-tert-butylstyrene methyl ether, distyryl methyl ether, 4- (2-pyridyl) styryl methyl ether, p-methoxyphenethyl methyl ether, 3, 5-dimethylstyrene methyl ether, 3, 4-dimethoxystyrene methyl ether, 3, 5-dimethoxystyrene methyl ether, 3,4, 5-trimethoxystyrene methyl ether, chroman-5-vinyl methyl ether, p-fluorophenylvinyl methyl ether, p-trifluoromethylstyrene methyl ether, 4-methoxycarbonylstyrene methyl ether, 4- (N, N-dimethyl) aminocarbonylstyrene methyl ether, 2-methylstyrene methyl styrene methyl ether, 4- (N, n-diethyl) amino-2-methoxybenzylvinylmethyl ether, 2-naphthylvinylmethyl ether, 1-naphthylvinylmethyl ether, 9-anthracenylvinylmethyl ether, 2-distyrylmethyl ether, α -methylbenzylvinylmethyl ether, 1, 4-benzenedivinylmethyl ether, 2-furanvinylmethyl ether, benzofuran-2-vinylmethyl ether, 6-methylpyridine-2-vinylmethyl ether, (N-methyl) imidazole-2-vinylmethyl ether, 5-pyrimidinylmethyl ether, 3-quinolinylmethyl ether, 2-quinolinylmethyl ether, (N-methyl) indole-3-vinylmethyl ether, indole-4-vinylmethyl ether, methyl ether, ethyl ether, propyl ether, ethyl ether, propyl ether, butyl ether, ethyl ether, 2-, Indole-7-vinylmethyl ether, (N-methyl) pyridopyrrole-3-vinylmethyl ether, (N-ethyl) carbazole-3-vinylmethyl ether.

The key technology of the invention is to provide a cheap and stable transition metal catalyst Ni (acac)₂Catalytic one-pot method for realizing the silicification of C-O bond of alkenyl methyl ether and the hydrogenation reaction process of carbon-carbon double bond, Et₃Si-Bpin and HSiEt₃Respectively used as a silicon-based reagent and a hydrogen source, simple and efficient reaction, and compatibility with various functional groups and heterocyclic frameworks.

Compared with the existing synthesis method for preparing the alkyl silicon compound by olefin hydrosilation, the synthesis method has the following characteristics:

(1) with cheap, stable divalent nickel Ni (acac)₂The catalyst is a commercial carbene ligand IMes & HCl which is taken as a ligand, the reaction process is simple to operate, and the practicability is high;

(2) the method can be applied to the preparation of straight-chain alkyl silicon compounds with single structures, and is also suitable for synthesizing alkyl silicon compounds with heteroatom functional groups such as nitrogen, oxygen, fluorine and the like or heterocyclic structures;

(3) the raw material is derived from aldehyde, and the alkenyl methyl ether compound is synthesized by one step through a Wittig reaction, so that the yield is high, and the source is wide;

(4) the reaction has high chemical selectivity, and can react with C-O bond and carbon-carbon double bond in specific alkenyl methyl ether without influencing other functional groups containing C-O bond or unsaturated double bond.

Drawings

FIG. 1 is a reaction scheme of a synthesis process provided by the present invention;

FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of example 1;

FIG. 3 is a NMR carbon spectrum of example 1;

FIG. 4 is a NMR hydrogen spectrum of example 2;

FIG. 5 is a NMR carbon spectrum of example 2.

Detailed Description

The technical solution of the present invention will be further specifically described below by way of examples.

The synthesis methods of the alkenyl methyl ether raw material 1 and the silicon boron reagent 2 used in the invention are disclosed in the literature (org. Lett.,2020,22, 6424; Organometallics,2008,27, 6013). Synthesis of the alkyl silicon Compound: into a dry 25mL Schlenk tube, Ni (acac) was added₂(0.03mmol), IMes & HCl (0.03mmol), Zn (0.06mmol) and K₃PO₄(0.45 mmol). The reaction tube was evacuated and refilled with nitrogen and repeated three times to ensure a nitrogen atmosphere for the reaction, and then anhydrous toluene (1.5mL), starting materials 1(0.3mmol), 2(0.6mmol) and HSiEt were added under nitrogen protection₃(0.9mmol), the stopcock of the reaction tube is screwed down, the reaction is carried out at 110 ℃ under the closed condition, the stirring is stopped after the continuous stirring for 24 hours,cooling to room temperature, transferring the reaction solution to a 25mL round-bottom flask, evaporating the solvent under reduced pressure, separating and purifying the crude product by column chromatography, taking the mixed solution of petroleum ether and ethyl acetate as eluent, carrying out nuclear magnetic detection on the obtained product, and weighing to calculate the reaction yield.

Example 1

The product is as follows: phenethyltriethylsilane

Into a 25mL Schlenk tube, Ni (acac) was added₂(0.03mmol,7.7mg), IMes & HCl (0.03mol,10.2mg), Zn (0.06mmol, 3.9mg) and K₃PO₄(0.45mmol,95.4 mg). The reaction tube was evacuated, charged with nitrogen three times, and then anhydrous toluene (1.5mL) was added. Substrate 1-1(0.3mmol,40.2mg), 2(0.6mmol,145.2mg) and HSiEt were added via syringe under nitrogen₃(0.9mmol,104.4 mg), the stopcock was screwed down and stirred at 110 ℃ for 24 h. After the reaction was stopped, the reaction mixture was cooled to room temperature, the solvent was distilled off under reduced pressure, and the product, i.e., a colorless liquid, was obtained by column chromatography using petroleum ether as an eluent to obtain 3-1(50.3mg, 76%) of a phenethyl product.¹H NMR(400MHz,CDCl₃)δ7.31– 7.25(m,3H),7.24–7.13(m,2H),2.65–2.56(m,2H),0.95(t,J＝7.9Hz,9H),0.92–0.85(m,2H),0.55(q,J＝ 7.9Hz,6H).¹³C NMR(101MHz,CDCl₃)δ145.6,128.3,127.7,125.4,30.0,13.6,7.4,3.2.

Example 2

The product is as follows: p-methyl phenethyl triethyl silane

The substrate was changed to compound 1-2(0.3mmol,44.4mg), and the synthesis method of example 1 was employed to give product 3-2(51.3mg, 73%) as a colorless liquid.¹H NMR(400MHz,CDCl₃)δ7.11(s,4H),2.64–2.54(m,2H),2.34(s,3H),0.98(t,J＝7.9 Hz,9H),0.92–0.85(m,2H),0.57(q,J＝7.9Hz,6H).¹³C NMR(101MHz,CDCl₃)δ142.6,134.8,128.9,127.5, 29.5,21.0,13.8,7.5,3.2.

Example 3

The product is as follows: m-methyl phenethyl triethyl silane

The substrate was changed to compound 1-3(0.3mmol,44.4mg), and the synthesis method of example 1 was employed to give product 3-3(49.4mg, 70%) as a colorless liquid.¹H NMR(400MHz,CDCl₃)δ7.20(t,J＝7.5Hz,1H),7.09–6.97(m,3H),2.65–2.56(m, 2H),2.37(s,3H),0.99(t,J＝7.9Hz,9H),0.95–0.87(m,2H),0.59(q,J＝7.9Hz,6H).¹³C NMR(101MHz, CDCl₃)δ145.6,137.8,128.5,128.2,126.2,124.7,29.9,21.4,13.7,7.5,3.2.

Example 4

The product is as follows: p-tert-butyl phenethyltriethylsilane

The substrate was changed to compound 1-4(0.3mmol,57.0mg) and the synthesis of example 1 was used to give product 3-4(71.1mg, 86%) as a colorless liquid using petroleum ether as eluent.¹H NMR(400MHz,CDCl₃)δ7.34(d,J＝8.3Hz,2H),7.18(d,J＝8.1 Hz,2H),2.66–2.57(m,2H),1.34(s,9H),0.99(t,J＝8.0Hz,9H),0.95–0.88(m,2H),0.59(q,J＝7.9Hz,6H). ¹³C NMR(101MHz,CDCl₃)δ148.2,142.5,127.3,125.1,34.3,31.4,29.4,13.5,7.5,3.3.

Example 5

The product is as follows: biphenylethyltriethylsilane

The substrate was changed to Compound 1-5(0.3mmol,63.0mg) by the synthetic method of example 1 to giveTo product 3-5(82.5mg, 93%), petroleum ether was used as eluent and the product was a colorless liquid.¹H NMR(400MHz,CDCl₃)δ7.63–7.58(m,2H),7.57–7.51(m,2H), 7.47–7.41(m,2H),7.37–7.27(m,3H),2.72–2.63(m,2H),1.04–0.91(m,11H),0.60(q,J＝7.9Hz,6H).¹³C NMR(101MHz,CDCl₃)δ144.8,141.2,138.4,128.7,128.1,127.04,126.97,126.9,29.7,13.6,7.5,3.3.

Example 6

The product is as follows: 4- (2-pyridyl) phenethyltrimethylsilane

The substrate was changed to compound 1-6(0.3mmol,63.3mg), and the synthesis method of example 1 was used to give product 3-6(75.9mg, 85%) as a colorless liquid using petroleum ether and ethyl acetate 50:1 as eluent.¹H NMR(400MHz,CDCl₃)δ8.68(dt,J＝4.8,1.4Hz, 1H),7.92(d,J＝8.2Hz,2H),7.77–7.67(m,2H),7.32(d,J＝8.2Hz,2H),7.19(ddd,J＝5.6,4.8,2.8Hz,1H), 2.72–2.63(m,2H),1.03–0.88(m,11H),0.58(q,J＝7.9Hz,6H).¹³C NMR(101MHz,CDCl₃)δ157.5,149.5, 146.6,136.7,136.6,128.1,126.8,121.7,120.2,29.8,13.5,7.4,3.2.

Example 7

The product is as follows: p-methoxyphenethyl triethylsilane

The substrate was changed to compound 1-7(0.3mmol,49.2mg) and the synthesis of example 1 was used to give product 3-7(58.3mg, 78%) as a colorless liquid using petroleum ether as eluent.¹H NMR(400MHz,CDCl₃)δ7.12(d,J＝8.5Hz,2H),6.82(d,J＝8.6 Hz,2H),3.79(s,3H),2.60–2.52(m,2H),0.95(t,J＝7.9Hz,9H),0.90–0.80(m,2H),0.54(q,J＝7.9Hz,6H). ¹³C NMR(101MHz,CDCl₃)δ157.5,137.7,128.5,113.7,55.3,29.1,13.8,7.5,3.2.

Example 8

The product is as follows: 3, 5-Dimethylphenylethyltriethylsilane

The substrate was changed to compound 1-8(0.3mmol,48.6mg) and the synthesis of example 1 was used to give product 3-8(58.2mg, 78%) as a colourless liquid with petroleum ether as eluent.¹H NMR(400MHz,CDCl₃)δ6.90–6.82(m,3H),2.64–2.51(m,2H), 2.33(s,6H),1.00(t,J＝7.9Hz,9H),0.95–0.86(m,2H),0.59(q,J＝7.9Hz,6H).¹³C NMR(101MHz,CDCl₃) δ145.6,137.7,127.1,125.5,29.8,21.3,13.8,7.5,3.2.

Example 9

The product is as follows: 3, 4-Dimethoxyphenethyltriethylsilane

The substrate was changed to compound 1-9(0.3mmol,58.2mg) and the synthesis method of example 1 was used to give 3-9(68.8mg, 82%) as a colorless liquid using petroleum ether and ethyl acetate 50:1 as eluent.¹H NMR(400MHz,CDCl₃)δ6.82–6.71(m,3H),3.89(s, 3H),3.86(s,3H),2.62–2.52(m,2H),0.96(t,J＝7.9Hz,9H),0.92–0.82(m,2H),0.55(q,J＝7.9Hz,6H).¹³C NMR(101MHz,CDCl₃)δ148.7,146.9,138.3,119.2,111.14,111.06,55.9,55.8,29.6,13.7,7.5,3.2.

Example 10

The product is as follows: 3, 5-Dimethoxyphenethyltriethylsilane

The substrate was changed to compound 1-10(0.3mmol,58.2mg), and the synthesis method of example 1 was used to give 3-10(71.2mg, 85%) as petroleum ether and ethyl acetate 5 ═ 50:1 is eluent, and the product is colorless liquid.¹H NMR(400MHz,CDCl₃)δ6.37(d,J＝2.3Hz,2H), 6.29(t,J＝2.3Hz,1H),3.79(s,6H),2.60–2.51(m,2H),0.96(t,J＝7.9Hz,9H),0.92–0.84(m,2H),0.55(q,J ＝8.0Hz,6H).¹³C NMR(101MHz,CDCl₃)δ160.7,148.1,105.7,97.4,55.2,30.3,13.4,7.5,3.2.HRMS m/z (ESI)calcdfor C₁₆H₂₉O₂Si(M+H)⁺281.1931,found281.1930.

Example 11

The product is as follows: 3,4, 5-trimethoxyphenethyltriethylsilane

The substrate was changed to compound 1-11(0.3mmol,67.2mg), and the synthesis method of example 1 was used to give product 3-11(80.1mg, 86%) as a colorless liquid using petroleum ether and ethyl acetate 20:1 as eluent.¹H NMR(400MHz,CDCl₃)δ6.42(s,2H),3.86(s,6H), 3.82(s,3H),2.60–2.53(m,2H),0.97(t,J＝7.9Hz,9H),0.92–0.83(m,2H),0.56(q,J＝7.9Hz,6H).¹³C NMR (101MHz,CDCl₃)δ153.0,141.4,135.8,104.5,60.9,56.0,30.4,13.5,7.5,3.2.

Example 12

The product is as follows: benzodihydrofuran-5-ethyltriethylsilane

The substrate was changed to compound 1-12(0.3mmol,52.8mg), and the synthesis method of example 1 was used to give product 3-12(55.1mg, 70%) as a colorless liquid using petroleum ether and ethyl acetate 100:1 as eluent.¹H NMR(400MHz,CDCl₃)δ7.05(s,1H),6.93(d,J ＝8.1Hz,1H),6.70(d,J＝8.0Hz,1H),4.54(t,J＝8.6Hz,2H),3.18(t,J＝8.6Hz,2H),2.58–2.50(m,2H), 0.96(t,J＝8.0Hz,9H),0.90–0.79(m,2H),0.55(q,J＝7.9Hz,6H).¹³C NMR(101MHz,CDCl₃)δ157.9,137.8, 126.9,126.8,124.1,108.8,71.1,29.8,29.4,14.2,7.5,3.3.

Example 13

The product is as follows: p-fluorophenethyl triethylsilane

The substrate was changed to compound 1-13(0.3mmol,45.6mg) and the synthesis of example 1 was used to give product 3-13(50.9mg, 71%) as a colorless liquid using petroleum ether as eluent.¹H NMR(400MHz,CDCl₃)δ7.15(dd,J＝8.5,5.6Hz,2H),6.96(t,J＝ 8.7Hz,2H),2.64–2.55(m,2H),0.96(t,J＝7.9Hz,9H),0.90–0.82(m,2H),0.55(q,J＝7.9Hz,6H).¹⁹F NMR (376MHz,CDCl₃)δ-118.5.¹³C NMR(101MHz,CDCl₃)δ161.0(d,J＝242.7Hz),141.1(d,J＝3.2Hz),128.9 (d,J＝7.7Hz),114.9(d,J＝21.0Hz),29.3,13.8,7.4,3.2.

Example 14

The product is as follows: p-trifluoromethylphenethyltriethylsilane

The substrate was changed to compound 1-14(0.3mmol,60.6mg) and the synthesis procedure of example 1 was used to give product 3-14(69.0mg, 80%) as a colorless liquid using petroleum ether as eluent.¹H NMR(400MHz,CDCl₃)δ7.53(d,J＝8.0Hz,2H),7.31(d,J＝8.0 Hz,2H),2.72–2.62(m,2H),0.97(t,J＝7.9Hz,9H),0.92–0.84(m,2H),0.57(q,J＝8.0Hz,6H).¹⁹F NMR (376MHz,CDCl₃)δ-62.2.13C NMR(101MHz,CDCl₃)δ149.7(d,J＝1.3Hz),128.0,127.8(q,J＝32.2Hz), 125.2(q,J＝3.8Hz),124.4(q,J＝271.6Hz),30.0,13.5,7.4,3.2.

Example 15

The product is as follows: 4-methoxycarbonylphenethyltriethylsilane

The substrate was changed to compound 1-15(0.3mmol,57.6mg), and the synthesis method of example 1 was used to give product 3-15(69.1mg, 83%) as a colorless liquid using petroleum ether and ethyl acetate as eluent (100: 1).¹H NMR(400MHz,CDCl₃)δ7.95(d,J＝8.3Hz,2H), 7.26(d,J＝8.2Hz,2H),3.90(s,3H),2.70–2.61(m,2H),0.96(t,J＝7.9Hz,9H),0.92–0.84(m,2H),0.56(q,J ＝7.9Hz,6H).¹³C NMR(101MHz,CDCl₃)δ167.2,151.1,129.7,127.7,127.5,51.9,30.2,13.4,7.4,3.2.

Example 16

The product is as follows: 4- (N, N-dimethylcarbamoyl) phenethyltriethylsilane

The substrate was changed to compound 1-16(0.3mmol,61.5mg) and the synthesis method of example 1 was used to give product 3-16(61.5mg, 70%) as a colorless liquid using petroleum ether and ethyl acetate 20:1 as eluent.¹H NMR(400MHz,CDCl₃)δ7.33(d,J＝8.1Hz,2H), 7.21(d,J＝8.1Hz,2H),3.09(s,3H),2.99(s,3H),2.66–2.57(m,2H),0.95(t,J＝7.9Hz,9H),0.90–0.83(m, 2H),0.55(q,J＝8.0Hz,6H).13C NMR(101MHz,CDCl3)δ171.8,147.2,133.4,127.6,127.2,39.6,35.4,29.9, 13.5,7.4,3.2.

Example 17

The product is as follows: 2-Methylphenylethyltriethylsilane

The substrate was changed to compound 1-17(0.3mmol,44.4mg) and the synthesis of example 1 was used to give product 3-17(33.1mg, 47%) as a colorless liquid using petroleum ether as eluent.¹H NMR(400MHz,CDCl₃)δ7.19–7.03(m,4H),2.62–2.52(m,2H), 2.29(s,3H),0.97(t,J＝7.9Hz,9H),0.86–0.77(m,2H),0.58(q,J＝8.0Hz,6H).¹³C NMR(101MHz,CDCl₃) δ143.7,135.2,130.1,127.9,126.0,125.6,27.4,19.1,12.5,7.5,3.3.

Example 18

The product is as follows: 2-methoxy-4- (N, N-diethyl) phenethyltriethylsilane

The substrate was changed to compound 1-18(0.3mmol,70.5mg) and the synthesis method of example 1 was used to give product 3-18(68.5mg, 71%) as a colorless liquid using petroleum ether and ethyl acetate 20:1 as eluent.¹H NMR(400MHz,CDCl₃)δ7.02(d,J＝7.9Hz,1H), 6.34–6.24(m,2H),3.84(s,3H),3.36(q,J＝7.0Hz,4H),2.62–2.46(m,2H),1.19(t,J＝7.1Hz,6H),1.00(t,J ＝7.9Hz,9H),0.90–0.81(m,2H),0.59(q,J＝7.9Hz,6H).¹³C NMR(101MHz,CDCl₃)δ158.0,147.4,129.1, 121.6,104.4,96.2,55.1,44.6,23.2,12.6,12.1,7.4,3.3.

Example 19

The product is as follows: 2-naphthylethyltriethylsilane

The substrate was changed to compound 1-19(0.3mmol,55.2mg) and the synthesis of example 1 was used to give product 3-19(72.8mg, 90%) as a colorless liquid using petroleum ether as eluent.¹H NMR(400MHz,CDCl₃)δ7.86–7.75(m,3H),7.66(s,1H),7.51– 7.35(m,3H),2.86–2.76(m,2H),1.08–0.96(m,11H),0.62(q,J＝7.9Hz,6H).¹³C NMR(101MHz,CDCl₃)δ 143.1,133.7,131.9,127.8,127.6,127.4,127.0,125.8,125.2,124.9,30.2,13.5,7.5,3.3.

Example 20

The product is as follows: 1-naphthylethyltriethylsilane

The substrate was changed to compound 1-20(0.3mmol,55.2mg) and the synthesis procedure of example 1 was used to give product 3-20(69.0mg, 85%) as a colorless liquid using petroleum ether as eluent.¹H NMR(400MHz,CDCl₃)δ8.04(d,J＝8.3Hz,1H),7.90–7.84(m, 1H),7.71(d,J＝7.9Hz,1H),7.56–7.45(m,2H),7.45–7.34(m,2H),3.13–3.04(m,2H),1.07–0.98(m,11H), 0.65(q,J＝7.9Hz,6H).¹³C NMR(101MHz,CDCl₃)δ141.7,133.9,131.5,128.8,126.2,125.7,125.6,125.3, 124.7,123.6,27.2,13.2,7.5,3.3.

Example 21

The product is as follows: 9-Anthranylethyltriethylsilane

The substrate was changed to compound 1-21(0.3mmol,70.2mg) and the synthesis of example 1 was used to give product 3-21(57.7mg, 60%) as a colorless liquid using petroleum ether as eluent.¹H NMR(400MHz,CDCl₃)δ8.32(s,1H),8.23(d,J＝8.8Hz,2H),8.01 (d,J＝8.0Hz,2H),7.56–7.42(m,4H),3.65–3.53(m,2H),1.16–1.03(m,11H),0.75(q,J＝7.9Hz,6H).¹³C NMR(101MHz,CDCl₃)δ138.2,131.7,129.3,128.7,125.3,125.2,124.8,124.1,22.1,14.2,7.7,3.3.

Example 22

The product is as follows: 2, 2-diphenyl tetraethyl silicon

The substrate was changed to compound 1-22(0.3mmol,63.0mg) and the synthesis procedure of example 1 was used to give product 3-22(44.4mg, 50%) as a colorless liquid using petroleum ether as eluent.¹H NMR(400MHz,CDCl₃)δ7.36–7.20(m,8H),7.17–7.10(m,2H), 4.06(t,J＝7.9Hz,1H),1.41(d,J＝7.9Hz,3H),0.82(t,J＝7.9Hz,9H),0.33(q,J＝7.9Hz,6H).¹³C NMR(101 MHz,CDCl₃)δ147.3,128.3,127.5,125.9,47.1,19.0,7.3,3.4.

Example 23

The product is as follows: alpha-methylphenylethyltriethylsilane

The substrate was changed to compound 1-23(0.3mmol,44.4mg) and the synthesis of example 1 was used to give product 3-23(42.6mg, 61%) as a colorless liquid using petroleum ether as eluent.¹H NMR(400MHz,CDCl₃)δ7.31–7.23(m,2H),7.21–7.12(m,3H), 2.89(dd,J＝13.7,3.4Hz,1H),2.25(dd,J＝13.7,11.9Hz,1H),1.16–1.04(m,1H),0.99(t,J＝7.9Hz,9H), 0.84(d,J＝7.4Hz,3H),0.60(q,J＝7.9Hz,6H).¹³C NMR(101MHz,CDCl₃)δ142.9,128.8,128.0,125.5,38.2, 19.2,13.8,7.7,2.2.

Example 24

1, 4-p-phenyl diethyl bis-triethyl silicon

Into a 25mL Schlenk tube, Ni (acac) was added₂(0.06mmol,15.4mg), IMes & HCl (0.06mol,20.4mg), Zn (0.12 mmol,7.8mg) and K₃PO₄(0.9mmol,190.8 mg). The reaction tube was evacuated, charged with nitrogen three times, and then anhydrous toluene (3.0mL) was added. Substrates 1-24(0.3mmol,57.0mg), 2(1.2mmol,290.4mg) and HSiEt were added via syringe under nitrogen₃(1.8mmol, 208.8mg), the stopcock was screwed down and stirred at 110 ℃ for 24 h. After the reaction was stopped, the reaction mixture was cooled to room temperature, the solvent was distilled off under reduced pressure, and the product, that is, 3 to 24(88.1mg, 81%) of phenethyl product was obtained by column chromatography using petroleum ether as an eluent, as a colorless liquid.¹H NMR(400MHz,CDCl₃)δ7.15(s, 4H),2.65–2.56(m,4H),0.99(t,J＝8.0Hz,18H),0.94–0.85(m,4H),0.58(q,J＝8.0Hz,12H).¹³C NMR(101 MHz,CDCl₃)δ142.7,127.6,29.5,13.7,7.5,3.3.

Example 25

The product is as follows: furan-2-ethyltriethylsilane

The substrate was changed to compound 1-25(0.3mmol,37.2mg) and the synthesis procedure of example 1 was used to give product 3-25(40.4mg, 64%) as a colorless liquid using petroleum ether as eluent.¹H NMR(400MHz,CDCl₃)δ7.29(d,J＝1.0Hz,1H),6.27(dd,J＝3.1, 1.9Hz,1H),5.98(dd,J＝3.1,1.0Hz,1H),2.67–2.57(m,2H),1.01–0.85(m,11H),0.53(q,J＝7.9Hz,6H). ¹³C NMR(101MHz,CDCl₃)δ158.7,140.5,110.1,103.7,22.3,9.5,7.4,3.1.

Example 26

The product is as follows: benzofuran-2-ethyl triethyl silicon

The substrate was changed to compound 1-26(0.3mmol,52.2mg) and the synthesis of example 1 was used to give product 3-26(29.0mg, 37%) as a colorless liquid using petroleum ether as eluent.¹H NMR(400MHz,CDCl₃)δ7.50–7.45(m,1H),7.42–7.38(m,1H), 7.22–7.13(m,2H),6.38(d,J＝1.0Hz,1H),2.81–2.72(m,2H),1.05–0.91(m,11H),0.57(q,J＝7.9Hz,6H). ¹³C NMR(101MHz,CDCl₃)δ162.0,154.6,129.0,123.0,122.3,120.1,110.6,100.8,22.9,9.4,7.4,3.1.

Example twenty-seven

The product is as follows: 6-methylpyridine-2-ethyl triethyl silicon

The substrate was changed to Compound 1-27(0.3mmol,44.7mg), and the synthesis of example 1 was followed to give product 3-27(50.7mg, 72%)) The product is colorless liquid with petroleum ether and ethyl acetate 50:1 as eluent.¹H NMR(400MHz,CDCl₃)δ7.46(t,J＝7.7Hz,1H), 6.98(d,J＝7.7Hz,1H),6.92(d,J＝7.6Hz,1H),2.80–2.71(m,2H),2.51(s,3H),1.00–0.89(m,11H),0.54(q, J＝7.9Hz,6H).¹³C NMR(101MHz,CDCl₃)δ164.1,157.4,136.5,120.2,118.4,32.6,24.5,11.7,7.4,3.2.

Example 28

The product is as follows: n-methylimidazole-2-ethyltriethylsilane

The substrate was changed to compound 1-28(0.3mmol,41.4mg) and the synthesis method of example 1 was used to give product 3-28(41.9mg, 62%) as a colorless liquid using petroleum ether and ethyl acetate 5:1 as eluent.¹H NMR(400MHz,CDCl₃)δ7.31(s,1H),7.13(s,1H), 3.84(s,3H),2.50–2.41(m,2H),0.94(t,J＝7.9Hz,9H),0.87–0.77(m,2H),0.53(q,J＝7.9Hz,6H).¹³C NMR (101MHz,CDCl₃)δ138.1,127.6,125.3,38.7,18.4,13.0,7.4,3.2.

Example 29

The product is as follows: pyrimidine-5-ethyl triethyl silicon

The substrate was changed to compound 1-29(0.3mmol,40.8mg) and the synthesis method of example 1 was used to give product 3-29(48.5mg, 73%) as a colorless liquid using petroleum ether and ethyl acetate 5:1 as eluent.¹H NMR(400MHz,CDCl₃)δ9.03(s,1H),8.57(s,2H), 2.63–2.55(m,2H),0.94(t,J＝7.9Hz,9H),0.90–0.83(m,2H),0.55(q,J＝7.9Hz,6H).¹³C NMR(101MHz, CDCl₃)δ156.4,156.1,138.0,24.9,13.1,7.3,3.1.

Example 30

The product is as follows: quinoline-3-ethyltriethylsilane

The substrate was changed to compound 1-30(0.3mmol,55.5mg), and the synthesis method of example 1 was used to give product 3-30(52.7mg, 65%) as a colorless liquid using petroleum ether and ethyl acetate 50:1 as eluent.¹H NMR(400MHz,CDCl₃)δ8.79(d,J＝2.3Hz,1H), 8.07(d,J＝8.4Hz,1H),7.92(d,J＝1.2Hz,1H),7.76(d,J＝8.1Hz,1H),7.64(ddd,J＝8.4,6.8,1.5Hz,1H), 7.50(ddd,J＝8.1,6.8,1.2Hz,1H),2.85–2.75(m,2H),1.03–0.93(m,11H),0.60(q,J＝7.9Hz,6H).¹³C NMR (101MHz,CDCl₃)δ151.9,146.7,137.9,133.0,129.1,128.3,128.2,127.2,126.4,27.5,13.3,7.4,3.2.

Example 31

The product is as follows: quinoline-2-ethyltriethylsilane

The substrate was changed to compound 1-31(0.3mmol,55.5mg) and the synthesis method of example 1 was used to give product 3-31(62.8mg, 77%) as a colorless liquid using petroleum ether and ethyl acetate 50:1 as eluent.¹H NMR(400MHz,CDCl₃)δ8.05(dd,J＝8.3,5.3Hz, 2H),7.76(dd,J＝8.1,1.4Hz,1H),7.67(ddd,J＝8.4,6.8,1.5Hz,1H),7.46(ddd,J＝8.1,6.9,1.2Hz,1H),7.33 (d,J＝8.5Hz,1H),3.02–2.92(m,2H),1.11–1.02(m,2H),0.98(t,J＝7.9Hz,9H),0.60(q,J＝7.9Hz,6H). ¹³C NMR(101MHz,CDCl₃)δ165.1,147.8,136.3,129.2,128.7,127.4,126.6,125.5,120.7,33.5,12.0,7.4,3.2.

Example 32

The product is as follows: n-methylindole-3-ethyltriethylsilane

Substrate was changed to compound 1-32(0.3mmol,56.1mg) using the example1 to give 3-32% (62.4mg, 76%) as a yellow liquid, eluting with 100:1 petroleum ether/ethyl acetate.¹H NMR(400MHz,CDCl₃)δ7.60(d,J＝7.9Hz,1H), 7.29(d,J＝8.2Hz,1H),7.22(t,J＝7.5Hz,1H),7.10(d,J＝14.8Hz,1H),6.85(s,1H),3.75(s,3H),2.80–2.70 (m,2H),1.05–0.94(m,11H),0.60(q,J＝7.9Hz,6H).¹³C NMR(101MHz,CDCl₃)δ137.1,127.5,125.3,121.4, 119.0,118.7,118.4,109.1,32.5,19.2,12.2,7.5,3.3.

Example 33

The product is as follows: indole-4-ethyl triethyl silicon

The substrate was changed to compound 1-33(0.3mmol,51.9mg), and the synthesis method of example 1 was used to give product 3-33(49.1mg, 63%) as a yellow liquid using petroleum ether and ethyl acetate 50:1 as eluent.¹H NMR(400MHz,CDCl₃)δ8.15(brs,1H),7.25(d,J ＝8.2Hz,1H),7.22–7.19(m,1H),7.17–7.10(m,1H),6.97(d,J＝7.1Hz,1H),6.59(ddd,J＝3.2,2.1,1.0Hz, 1H),2.95–2.86(m,2H),1.08–0.94(m,11H),0.61(q,J＝7.9Hz,6H).¹³C NMR(101MHz,CDCl₃)δ138.0, 135.7,126.6,123.4,122.2,118.0,108.6,100.9,27.5,12.8,7.5,3.3.

Example 34

The product is as follows: indole-7-ethyl triethyl silicon

The substrate was changed to compound 1-34(0.3mmol,51.9mg), and the synthesis method of example 1 was used to give product 3-34(61.9mg, 76%) as a yellow liquid using petroleum ether and ethyl acetate 50:1 as eluent.¹H NMR(400MHz,CDCl₃)δ8.08(brs,1H),7.50(dd, J＝6.6,2.4Hz,1H),7.22(t,J＝2.8Hz,1H),7.12–7.04(m,2H),6.58(dd,J＝3.2,2.0Hz,1H),2.90–2.80(m, 2H),1.10–0.90(m,11H),0.61(q,J＝7.9Hz,6H).¹³C NMR(101MHz,CDCl₃)δ134.4,127.62,127.60,123.6, 120.3,120.0,118.4,103.1,25.2,11.2,7.5,3.3.

Example 35

The product is as follows: n-methylpyridopyrrole-3-ethyltriethylsilicane

The substrate was changed to compound 1-35(0.3mmol,56.4mg) and the synthesis method of example 1 was used to give product 3-35(68.5mg, 83%) as a yellow liquid using petroleum ether and ethyl acetate 20:1 as eluent.¹H NMR(400MHz,CDCl₃)δ8.31(dd,J＝4.7,1.5Hz, 1H),7.87(dd,J＝7.8,1.6Hz,1H),7.02(dd,J＝7.8,4.7Hz,1H),6.96(d,J＝1.2Hz,1H),3.83(s,3H),2.77– 2.68(m,3H),1.02–0.92(m,11H),0.58(q,J＝7.9Hz,6H).¹³C NMR(101MHz,CDCl₃)δ148.1,142.6,126.9, 125.2,119.9,117.0,114.5,30.9,19.3,12.0,7.5,3.2.

Example 36

The product is as follows: n-ethyl carbazole-3-ethyl triethyl silicane

The substrate was changed to compound 1-36(0.3mmol,75.3mg), and the synthesis method of example 1 was used to give product 3-36(85.7mg, 85%) as a yellow liquid using petroleum ether and ethyl acetate 50:1 as eluent.¹H NMR(400MHz,CDCl₃)δ8.09(d,J＝7.8Hz,1H), 7.93(s,1H),7.48–7.31(m,4H),7.20(ddd,J＝7.9,7.0,1.1Hz,1H),4.36(q,J＝7.2Hz,2H),2.86–2.77(m, 2H),1.42(t,J＝7.2Hz,3H),1.16–0.94(m,11H),0.60(q,J＝7.9Hz,6H).¹³C NMR(101MHz,CDCl₃)δ140.1, 138.3,136.2,125.7,125.3,122.9,122.8,120.3,118.9,118.4,108.3,108.1,37.5,30.0,14.6,13.8,7.5,3.3。