Functionalization of Tetraorganosilanes and Permethyloligosilanes at a Methyl Group on Silicon via Iridium-Catalyzed C(sp3)–H Borylation
摘要:
In the presence of an iridium 3,4,7,8-tetramethyl-1,10-phenanthroline catalyst, a methyl group on the silicon atom of alkyltrimethylsilanes undergoes selective C-H borylation with bis(pinacolato)diboron in cyclooctane at 135 degrees C to give alkyl(borylmethyl)dimethylsilanes. The C-H borylation of tetramethylsilane takes place efficiently at 100 degrees C. Permethyloligosilanes can also undergo C-H borylation without cleavage of the Si-Si bonds.
[EN] PROCESS FOR THE STEPWISE SYNTHESIS OF SILAHYDROCARBONS<br/>[FR] PROCÉDÉ DE SYNTHÈSE SÉQUENTIELLE DE SILAHYDROCARBURES
申请人:MOMENTIVE PERFORMANCE MAT INC
公开号:WO2021243137A1
公开(公告)日:2021-12-02
The invention relates to a process for the stepwise synthesis of silahydrocarbons bearing up to four different organyl substituents at the silicon atom, wherein the process includes at least one step a) of producing a bifunctional hydridochlorosilane by a redistribution reaction, selective chlorination of hydridosilanes with an ether/HCI reagent, or by selective chlorination of hydridosilanes with SiCI4, at least one step b) of submitting a bifunctional hydridochloromonosilane to a hydrosilylation reaction, at least one step c) of hydrogenation of a chloromonosilane, and a step d) in which a silahydrocarbon compound is obtained in a hydrosilylation reaction.
本发明涉及一种逐步合成在硅原子上带有最多四种不同有机基团取代的硅氢化物的过程,其中该过程包括至少以下步骤:a) 通过重分配反应、使用醚/HCI试剂对氢硅烷进行选择性氯化,或者通过使用四氯化硅对氢硅烷进行选择性氯化来制备双功能氢氯硅烷;至少一个步骤 b) 将双功能氢氯单硅烷进行氢硅化反应;至少一个步骤 c) 对氯代单硅烷进行氢化;以及步骤 d) 在氢硅化反应中获得硅氢化物化合物。
Reactivity of Hypervalent Species: Reactions of Anionic Penta-Coordinated Silicon Complexes towards Nucleophiles
作者:Alain Boudin、Geneviève Cerveau、Claude Chuit、Robert J. P. Corriu、Catherine Reye
DOI:10.1246/bcsj.61.101
日期:1988.1
The reactivity of anionic penta-coordinated silicon complexes [RSi(O2C6H4-o)2]−Na+ 1 with nucleophilic reagents has been studied. 1 can be reduced to organosilanes RSiH3 by metallic hydrides. Reactions with an excess of Grignard or organolithium reagents (R′MgX or R′Li) gave tetraorganosilanes RSiR′3. When only two molar equivalents of Grignard reagents (R′MgX) or lithium reagents (R′Li) are added
This invention relates to a process for preparing tetrahydrocarbylsilane in high yield, comprising: a) forming a reaction mass from molten metal and trihydrocarbylaluminum, in an hydrocarbon solvent under an inert gas atmosphere; b) maintaining the reaction mass at a temperature in the range of from about 100.degree. to about 130.degree. C. for a period of time sufficient to form sodium tetrahydrocarbylaluminate; c) contacting the sodium tetrahydrocarbylaluminate with organotrihalosilane; and d) heating the contacted tetrahydrocarbylaluminate and organotrihalosilane to a temperature and for a period of time sufficient to form the tetrahydrocarbylsilane, wherein the tetrahydrocarbylaluminate and tetrahydrocarbylsilane are formed at a pressure of less than about 3000 KPa and wherein the hydrocarbyl group of the tetrahydrocarbyl silane is one or a mixture of hydrocarbyl groups having less than about 8 carbon atoms each.