Branch-Selective Addition of Unactivated Olefins into Imines and Aldehydes
Branch-Selective Addition of Unactivated Olefins into Imines and Aldehydes
复制标题
DOI：
10.1021/jacs.8b11699
复制
发表时间：
2018-12-12
影响因子：
15
通讯作者：
Shenvi, Ryan A.
中科院分区：
文献类型：
--
作者：
Matos, Jeishla L. M.;Vasquez-Cespedes, Suhelen;Shenvi, Ryan A.
使用金属氢化物氢原子转移（MHAT）催化剂来偶联烯烃和胜任的亲自由基亲电体，自由基氢官能化容易地发生。传统的双电子亲电试剂保持不反应。本文报道了无电子偏置的烯烃与亚胺和醛的还原偶联反应。铁催化允许通过自由基的中间作用将烷基取代的烯烃加成到亚胺中，而催化Co（Sal（t-Bu，t-Bu））和铬盐的组合通过形成推定的烷基铬中间体使烯烃和醛的支链选择性偶联成为可能。
Radical hydrofunctionalization occurs with ease using metal-hydride hydrogen atom transfer (MHAT) catalysis to couple alkenes and competent radicalophilic electrophiles. Traditional two-electron electrophiles have remained unreactive. Herein we report the reductive coupling of electronically unbiased olefins with imines and aldehydes. Iron catalysis allows addition of alkyl-substituted olefins into imines through the intermediacy of free radicals, whereas a combination of catalytic Co(Sal(t-Bu,t-Bu)) and chromium salts enables a branch-selective coupling of olefins and aldehydes through the formation of a putative alkyl chromium intermediate.