Cobalt-Catalyzed Regio- and Stereoselective Hydrosilylation of Alk-2-ynes with Tertiary Silanes
作者:Hongfang Li、Chengbo Yang、Dongyang Wang、Liang Deng
DOI:10.1021/acs.organomet.2c00563
日期:——
Selectivity control in the addition reactions of internal alkynes that bear two similar substituents presents a big challenge in modern organic synthesis. Herein we report that β-(E)-selective hydrosilylation of alk-2-ynes with tertiary silanes can be achieved by using Co2(CO)8 as the catalyst. Under the catalytic reaction conditions, a wide range of alk-2-ynes can be converted into vinylsilanes with
带有两个相似取代基的内部炔烃加成反应的选择性控制对现代有机合成提出了巨大的挑战。在此我们报道了通过使用Co 2 (CO) 8作为催化剂可以实现烷-2-炔与叔硅烷的β-( E )-选择性氢化硅烷化。在催化反应条件下,多种烷-2-炔可以转化为乙烯基硅烷,其中β-( E )异构体作为主要或唯一的氢化硅烷化产物。机理研究表明炔桥二钴物质是可能的中间体。烯基桥联二钴甲硅烷基中间体中取代基之间的空间排斥被认为是引起观察到的区域选择性的关键因素。