Gan Yi, Xu Wei, Liu Yuanhong
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 Lu , Shanghai 200032 , People's Republic of China.
Org Lett. 2019 Dec 6;21(23):9652-9657. doi: 10.1021/acs.orglett.9b03822. Epub 2019 Nov 19.
The first Ni/Cu-catalyzed regiodivergent synthesis of allylsilanes directly from allylic alcohols through modulating the steric and electronic properties of the ligands on the nickel catalyst has been developed. Good yields and excellent selectivity were obtained regardless of whether linear or α-branched allylic alcohols were utilized. Mechanistic studies indicate that an allyloxyboronate species is formed during the reaction, which likely serves as an activated intermediate toward the oxidative addition of the C(allyl)-O bond.
通过调节镍催化剂上配体的空间和电子性质，首次开发了直接从烯丙醇出发的镍/铜催化的区域发散性烯丙基硅烷合成方法。无论使用的是直链还是α-支链烯丙醇，都能获得良好的产率和优异的选择性。机理研究表明，反应过程中形成了烯丙氧基硼酸酯物种，它可能作为C(烯丙基)-O键氧化加成的活性中间体。
