Wen Huanan, Wan Xiaolong, Huang Zheng
State Key Laboratory of Organometallic Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Rd, Shanghai, 200032, China.
Angew Chem Int Ed Engl. 2018 May 22;57(21):6319-6323. doi: 10.1002/anie.201802806. Epub 2018 Apr 25.
The strategic carbon-to-silicon substitution at a stereogenic center can produce chiral silanes with significantly improved properties relative to their carbon congeners. We herein report an unprecedented cobalt-catalyzed asymmetric hydrosilylation of unsymmetric alkynes with dihydrosilanes that furnishes silicon-stereogenic vinylhydrosilanes with high regio- and enantioselectivity. The absolute configurations of the products were determined by chiroptical methods in combination with DFT calculations. The synthetic versatility of the vinylhydrosilanes as chiral building blocks was further demonstrated by asymmetric Si-H insertion and catalytic hydroboration reactions.
在一个手性中心进行战略性的碳到硅取代，可以产生相对于其碳同系物具有显著改善性能的手性硅烷。我们在此报告了一种前所未有的钴催化不对称硅氢化反应，该反应使用二氢硅烷对不对称炔烃进行硅氢化，以高区域选择性和对映选择性提供硅手性乙烯基氢硅烷。通过圆二色光谱方法结合密度泛函理论计算确定了产物的绝对构型。乙烯基氢硅烷作为手性结构单元的合成多功能性通过不对称硅氢插入反应和催化硼氢化反应得到了进一步证明。
