南方科技大学Chuan He研究小组近日利用硅-氢/氮-氢的催化不对称脱氢偶联反应，成功实现了硅立体中心的硅氮烷合成。该研究于2023年5月19日发表于国际一流学术期刊《美国化学会杂志》上。

在该研究中，团队报道通过催化苯胺和二氢硅烷的脱氢偶联反应，实现了一个高度手性选择性的含硅立体中心的硅氮烷合成。这个反应很容易以高收率和高手性选择性（高达99% ee）产生各种手性硅氮烷和二硅氮烷。这个反应的效用在构建以主链硅立体中心手性为特点的聚碳硅氮烷中得到了进一步证明。

此外，经过手性富集的硅氮烷只要简单反应就可转化为各种具有特别手性的手性硅烷化合物，展示出在合成新型含硅功能分子砌块方面的潜在价值。

据了解，尽管在合成硅氮烷上有越来越多的进展，含硅立体中心的催化不对称合成等方面的探索明显更少，仍然是一个值得被关注的挑战。

附：英文原文

Title: Catalytic Asymmetric Dehydrogenative Si–H/N–H Coupling: Synthesis of Silicon-Stereogenic Silazanes

Author: Meng-Meng Liu, Yankun Xu, Chuan He

Issue&Volume: May 19, 2023

Abstract: Despite growing progress in the construction of silazanes, the catalytic asymmetric synthesis of silicon-stereogenic silazanes is significantly less explored and remains a considerable challenge. Herein, we report a highly enantioselective synthesis of silicon-stereogenic silazanes via catalytic dehydrogenative coupling of dihydrosilanes with anilines. The reaction readily produces a wide range of chiral silazanes and bis-silazanes in excellent yields and stereoselectivities (up to 99% ee). Further utility of this process is demonstrated by the construction of polycarbosilazanes featuring configurational main chain silicon-stereogenic chirality. In addition, the straightforward transformation of the enantioenriched silazanes delivers various chiral silane compounds in a stereospecific fashion, illustrating their potential utilities as synthons for the synthesis of novel silicon-containing functional molecules.

DOI: 10.1021/jacs.3c02263

Source: https://pubs.acs.org/doi/10.1021/jacs.3c02263