Zhao Binzhi, Li Yuqiang, Li Haoyang, Belal Md, Zhu Lei, Yin Guoyin
The Institute for Advanced Studies, Wuhan University, Wuhan 430072, China.
Institute of Biomedical Materials Industry Technology, Hubei Engineering University, Xiaogan 432000, China.
Sci Bull (Beijing). 2021 Mar 30;66(6):570-577. doi: 10.1016/j.scib.2020.10.001. Epub 2020 Oct 6.
Synthesis of organosilanes from alkenes is a very important topic owing to their wide applications. A Ni/Cu dual metal-catalyzed arylsilylation of terminal alkenes, featuring migratory selectivity, has been developed. A wide diversity of aliphatic silanes have been prepared from terminal alkenes, aryl halides and Suginome's reagent. This protocol is highlighted by excellent regioselectivity, mild reaction conditions and good functional group tolerance. In addition to benzylic positions, carbon-carbon bonds can also be constructed at allylic positions. Preliminary mechanistic studies suggest that the copper cocatalyst promotes the transmetalation of Suginome's reagent, and the addition of a PyrOx ligand inhibits the formation of side-products from the carbon-Heck pathway. Moreover, studies toward the nature of the PyrOx ligand revealed that the steric hindrance of the oxazoline moiety greatly affects the chain-walking process, but not the arylation step.
由于有机硅烷的广泛应用，从烯烃合成有机硅烷是一个非常重要的课题。已经开发了一种具有迁移选择性的镍/铜双金属催化的末端烯烃芳基硅基化反应。从末端烯烃、芳基卤化物和杉野试剂制备了各种各样的脂肪族硅烷。该方法具有优异的区域选择性、温和的反应条件和良好的官能团耐受性。除了苄基位置外，还可以在烯丙基位置构建碳-碳键。初步机理研究表明，铜助催化剂促进了杉野试剂的金属转移，并且添加PyrOx配体抑制了碳-赫克途径副产物的形成。此外，对PyrOx配体性质的研究表明，恶唑啉部分的空间位阻对链行走过程有很大影响，但对芳基化步骤没有影响。
