Synergistic Ni/Cu catalyzed migratory arylsilylation of terminal olefins  

镍/铜协同催化的末端烯烃的迁移芳硅化反应

作　　者：Binzhi Zhao Yuqiang Li Haoyang Li MdBelal Lei Zhu Guoyin Yin 赵斌治;李玉强;李浩阳;Md.Belal;朱磊;阴国印(The Institute for Advanced Studies,Wuhan University,Wuhan 430072,China;Institute of Biomedical Materials Industry Technology,Hubei Engineering University,Xiaogan 432000,China)

机构地区：[1]The Institute for Advanced Studies,Wuhan University,Wuhan 430072,China [2]Institute of Biomedical Materials Industry Technology,Hubei Engineering University,Xiaogan 432000,China

出　　处：《Science Bulletin》2021年第6期570-577,M0004,共9页科学通报（英文版）

基　　金：supported by the National Natural Science Foundation of China(21702151,21774029,and 21871211);the Fundamental Research Funds for Central Universities(2042019kf0208)。

摘　　要：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 Pyr Ox ligand inhibits the formation of side-products from the carbon-Heck pathway.Moreover,studies toward the nature of the Pyr Ox ligand revealed that the steric hindrance of the oxazoline moiety greatly affects the chain–walking process,but not the arylation step.有机硅化物的广泛应用,引起了人们对有机硅的合成的广泛研究,其中用烯烃合成有机硅烷是一个非常重要的研究方向.本文发展了一个镍/铜双金属催化的末端烯烃的迁移选择性芳硅化反应,一步反应同时向烯烃引入芳基和硅基两个基团.通过此方法,可以从末端烯烃、芳基卤化物和Suginome试剂制备多种烷基取代的硅烷.该反应具有良好的区域选择性、温和的反应条件和良好的官能团兼容性的优点.除苄位外,也可以在烯丙位构建碳-碳键.初步的机理研究表明,铜助催化剂促进了Suginome试剂向镍的转金属,吡啶噁唑啉配体的存在可抑制烯烃插入芳基镍物种产生的副产物.此外,对吡啶噁唑啉类配体的研究表明,噁唑啉部分的位阻对链行走过程有极大的影响,但不对后续的芳基化造成影响.

关 键 词：Alkene difunctionalization Arylsilylation Synergistic catalysis Regioselectivity Metal migration 

分 类 号：TQ264.1[化学工程—有机化工]