Heteroatom-Directed Alkylcyanation of Alkynes
Heteroatom-Directed Alkylcyanation of Alkynes
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DOI：
10.1021/ja1017078
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发表时间：
2010-07-28
影响因子：
15
通讯作者：
Hiyama, Tamejiro
中科院分区：
文献类型：
--
作者：
Nakao, Yoshiaki;Yada, Akira;Hiyama, Tamejiro
发现在γ位具有杂原子（例如氮、氧和硫）的烷腈通过镍/路易斯酸催化立体选择性和区域选择性地与炔烃加成，得到高度取代的丙烯腈。杂原子官能团可能与镍中心配位，使烷基氰化物的C-CN键的氧化加成在动力学上有利，形成五元镍环中间体，从而防止β-氢化物消除以进行烷基氰化反应。
Alkanenitriles having a heteroatom such as nitrogen, oxygen, and sulfur at the gamma-position are found to add across alkynes stereo- and regioselectively by nickel/Lewis acid catalysis to give highly substituted acrylonitriles. The heteroatom functionalities likely coordinate to the nickel center to make oxidative addition of the C-CN bonds of the alkyl cyanides kinetically favorable, forming a five-membered nickelacycle intermediate and, thus, preventing beta-hydride elimination to allow the alkylcyanation reaction.