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钴催化的二烯烃迁移异构化反应。

Cobalt-Catalyzed Migration Isomerization of Dienes.

作者信息

Zhao Jiajin, Xu Guoxiong, Wang Xue, Liu Jiren, Ren Xiang, Hong Xin, Lu Zhan

机构信息

Department of Chemistry, Zhejiang University, Hangzhou 310058, China.

Center of Chemistry for Frontier Technologies, Department of Chemistry, Zhejiang University, Hangzhou 310058, China.

出版信息

Org Lett. 2022 Jul 1;24(25):4592-4597. doi: 10.1021/acs.orglett.2c01701. Epub 2022 Jun 21.

Abstract

A cobalt-catalyzed multipositional isomerization of conjugated dienes has been reported for the first time using an 8-oxazoline iminoquinoline ligand. This reaction is operationally simple and atom-economical using readily available starting materials with an mixture to access disubstituted 1,3-dienes with excellent yields and good , stereoselectivity. The mechanism via alkene insertion of cobalt hydride species and β-H elimination of a π-allyl cobalt intermediate is proposed on the basis of deuterium labeling and control experiments and density functional theory calculations.

摘要

首次报道了使用8-恶唑啉亚氨基喹啉配体的钴催化共轭二烯的多位异构化反应。该反应操作简单且原子经济,使用容易获得的起始原料和混合物,以优异的产率和良好的立体选择性得到二取代的1,3-二烯。基于氘标记、对照实验和密度泛函理论计算,提出了通过氢化钴物种的烯烃插入和π-烯丙基钴中间体的β-H消除的反应机理。

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