Hydrosilylation of cyclohexene, 1-methylcyclohexene, and isopropylidenecyclohexane
作者:O. G. Yarosh、L. V. Zhilitskaya、N. K. Yarosh、A. I. Albanov、M. G. Voronkov
DOI:10.1007/s11176-005-0114-4
日期:2004.12
Hydrosilylation of cyclohexene and isopropylidenecyclohexane with chloro(methyl)silanes Me3−n SiHCln (n = 1–3) gives rise to cyclohexyl- and chloro(2-cyclohexylpropyl)methylsilanes. Hydrosilylation of 1-methylcyclohexene with chlorodimethylsilane (n = 1) occurs anomalously and involves double-bond migration to form a mixture of seven compounds: the cis and trans isomers of 2-, 3-, 4-chlorodimethyl(methylcyclohexyl)silanes and chlorodimethyl(cyclohexylmethyl)silane. Chlorodimethylsilane (n = 2) adds to 1-methylcyclohexene to form a mixture of the cis and trans isomers of dichloro(methyl)(2-methylcyclohexyl)silane and dichloro(cyclohexylmethyl)methylsilane. With trichlorosilane (n = 3), no other products than trichloro(cyclohexylmethyl)silane are formed. The hydrosilylation products were reacted with ethynylmagnesium bromide to synthesize the corresponding ethynyl derivatives.
Aluminumchloride can be utilized as an active catalyst for the highly regioselective hydrosilylation of 1-alkyl, 1-aryl, 1,1-dialkyl, and cyclic cyclopropanes with chlorodimethylsilane in hexane at room temperature.