Method for preparing novel vinyl silicon compound

A technology of vinyl silicon and compounds, which is applied in the field of preparation of new vinyl silicon compounds, can solve the problems of β-type vinyl silicon compounds that have not been reported publicly, and achieve mild reaction conditions and high reaction efficiency Effect

Inactive Publication Date: 2018-09-28
DALIAN UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Although some methods for changing the regioselectivity and stereoselectivity of internal alkyne hydrosilylation reactions have been reported, there is no public report on the preparation technology of (Z)-β-type vinyl silicon-based compounds.

Method used

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  • Method for preparing novel vinyl silicon compound
  • Method for preparing novel vinyl silicon compound
  • Method for preparing novel vinyl silicon compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0021] Example 1: Preparation of (Z)-3(2-phenyl-2-(triethylsilyl)vinyl)oxazolidin-2-one

[0022] Under nitrogen, 3-phenylethynyl-pyrazolin 2-one (0.2mmol, 37.4mg) was dissolved in acetonitrile (2mL), then triethylsilane (0.4mmol, 46.4mg) and [Rh( CO) 2 Cl] 2 (0.005mmol, 1.9mg), the reaction mixture was stirred at room temperature, and reacted for 12h. After the reaction, column chromatography separated to obtain 46.1mg of a yellow oily product, Z / E=15:1, and the yield was 76%.

[0023]

[0024] 1 H NMR (400MHz, CDCl 3 ,TMS):δ7.29-7.25(m,2H),7.22-7.20(m,1H),7.11-7.08(m,2H),6.65(s,1H),4.42(t,J=8.0Hz,2H ), 3.85(t, J=8.0Hz, 2H), 0.92(t, J=8.0Hz, 9H), 0.65(q, J=8.0Hz, 6H). 13 C NMR (125MHz, CDCl 3 ): δ157.4, 143.7, 136.7, 136.0, 128.0, 128.0, 126.0, 62.1, 47.4, 7.6, 4.4. -1 .HRMS(EI-TOF)m / z:[M] + Calcd for C 17 h 25 NO 2 Si 303.1655; Found 303.1664.

Embodiment 2

[0025] Example 2: Preparation of (Z)-3(2-(4-methoxyphenyl)-2-(triethylsilyl)vinyl)oxazolidin-2-one

[0026] Under nitrogen, 3-p-methoxyphenylethynyl-pyrazolin 2-one (0.2 mmol, 43.4 mg) was dissolved in acetonitrile (2 mL) and triethylsilane (0.4 mmol, 46.4 mg) was added and [Rh(CO) 2 Cl] 2 (0.005mmol, 1.9mg), the reaction mixture was stirred at room temperature, and reacted for 12h. After the reaction, column chromatography separated to obtain 46.6mg of yellow oily product, Z / E>20:1, and the yield was 70%.

[0027]

[0028] 1 H NMR (500MHz, CDCl 3 , TMS): δ7.02(d, J=10.0Hz, 2H), 6.81(d, J=10.0Hz, 2H), 6.60(s, 1H), 4.41(t, J=10.0Hz, 2H), 3.82 (t,J=10.0Hz,2H),3.80(s,3H),0.92(t,J=10.0Hz,9H),0.65(q,J=10.0Hz,6H). 13 C NMR (125MHz, CDCl 3 ): δ158.0, 157.5, 136.6, 135.9, 129.8, 129.0, 113.4, 62.1, 56.2, 47.5, 7.6, 4.3. -1 .HRMS(EI-TOF)m / z:[M] + Calcd for C 18 h 27 NO 3 Si 333.1760; Found 333.1764.

Embodiment 3

[0029] Example 3: Preparation of (Z)-3(2-(4-chlorophenyl)-2-(triethylsilyl)vinyl)oxazolidin-2-one

[0030] Under nitrogen, 3-p-chlorophenylethynyl-pyrazolin 2-one (0.2 mmol, 44.2 mg) was dissolved in acetonitrile (2 mL), and triethylsilane (0.4 mmol, 46.4 mg) and [ Rh(CO) 2 Cl] 2 (0.005mmol, 1.9mg), the reaction mixture was stirred at room temperature, and reacted for 12h. After the reaction, column chromatography separated to obtain 46.5mg of a yellow oily product, Z / E=18:1, and the yield was 69%.

[0031]

[0032] 1 H NMR (500MHz, CDCl 3 , TMS): δ7.24(d, J=10.0Hz, 2H), 7.02(d, J=10.0Hz, 2H), 6.65(s, 1H), 4.42(t, J=10.0Hz, 2H), 3.85 (t,J=10.0Hz,2H),0.92(t,J=10.0Hz,9H),0.64(q,J=10.0Hz,6H). 13 C NMR (125MHz, CDCl 3 ): δ157.3, 142.3, 137.1, 134.2, 132.0, 129.4, 128.1, 62.1, 47.2, 7.6, 4.4. IR (KBr) ν2957, 2305, 1762, 1481, 1264, 749, 705cm - 1 .HRMS(EI-TOF)m / z:[M] + Calcd for C 17 h 24 ClNO 2 Si 337.1265; Found 337.1257.

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Abstract

The invention belongs to the technical field of organic synthesis and provides a method for preparing a novel vinyl silicon compound. The method comprises the following step: in an organic solvent, catalyzing a ynamine compound and an organosilane compound under the action of a tetracarbonyl rhodium dichloride dimer [Rh(CO)2Cl]2 catalyst, thereby obtaining a (Z)-beta-vinyl silicon compound. The method for preparing the (Z)-beta-vinyl silicon compound is mild in reaction condition, and the product yield is not less than 65%. The method is mild in reaction condition, green and high in reaction efficiency, and is relatively well applicable to on-scale production requirements, and the prepared (Z)-beta-vinyl silicon compound can be converted into multiple medicine intermediates.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, and relates to a preparation method of a novel vinyl silicon-based compound. Background technique [0002] Vinyl silicon-based compounds are an important class of organic synthesis intermediates, which can be used to synthesize organic drug intermediates with various structures through cross-coupling reactions, Tamao-Fleming oxidation reactions, electrophilic substitution reactions, and group transfer polymerization. In recent years, a series of documents or patents have reported the preparation methods of vinyl silicon-based compounds. [0003] Hydrosilylation of alkynes with silanes is the most direct and atom-economical method (J.Am.Chem.Soc.2015,137,6857. and Angew.Chem.Int.Ed.,2012,51,3225) , this reaction has received extensive research and attention. However, for the hydrosilation reaction of internal alkynes, four mixed vinyl silicon-based compounds of Z / E and α / β are generate...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F7/08
CPCC07F7/0812C07F7/0829
Inventor 宋汪泽郑楠李明郑玉斌
Owner DALIAN UNIV OF TECH
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