Inoue Atsushi, Kondo Junichi, Shinokubo Hiroshi, Oshima Koichiro
Department of Material Chemistry Graduate School of Engineering, Kyoto University Kyoto 606-8501, Japan.
Chemistry. 2002 Apr 2;8(7):1730-40. doi: 10.1002/1521-3765(20020402)8:7<1730::aid-chem1730>3.0.co;2-6.
The reaction of gem-dibromocyclopropanes 5 with nBu(3)MgLi affords butylated cyclopropylmagnesium species that can be trapped with various electrophiles. The reaction of dibromomethylsilanes 12 requires the addition of a catalytic amount of CuCN small middle dot2 LiCl for smooth migration of the alkyl groups. The resultant alpha-silylpentylmagnesium compounds 16 react with electrophiles, such as acyl chlorides or alpha,beta-unsaturated ketones to afford alpha- or gamma-silyl ketones, respectively. Treatment of dibromodisilylmethanes with Me(3)MgLi yields 1-bromo-1,1-disilylethanes 25 that can be converted into 1,1-disilylethenes 29 by dehydrobromination.
偕二溴环丙烷5与正丁基三甲基锂反应生成丁基化的环丙基镁物种，该物种可被各种亲电试剂捕获。二溴甲基硅烷12的反应需要加入催化量的氰化亚铜·二氯化锂以实现烷基的顺利迁移。所得的α-硅基戊基镁化合物16与亲电试剂（如酰氯或α,β-不饱和酮）反应，分别得到α-或γ-硅基酮。用甲基三甲基锂处理二溴二硅基甲烷得到1-溴-1,1-二硅基乙烷25，通过脱溴化氢反应可将其转化为1,1-二硅基乙烯29。
