Salen钴配合物催化自由基反应的研究进展  

Recent advances in CoSalen-catalyzed radical reactions

作　　者：殷允念 欧阳冬晨 王俊杰 朱戎 Yun-Nian Yin;Dong-Chen Ouyang;Jun-Jie Wang;Rong Zhu(Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education,Beijing National Laboratory for Molecular Sciences,College of Chemistry and Molecular Engineering,Peking University,Beijing 100871,China)

机构地区：[1]北京大学化学与分子工程学院,北京分子科学国家研究中心,生物有机与分子工程教育部重点实验室,北京100871

出　　处：《中国科学：化学》2020年第10期1217-1232,共16页SCIENTIA SINICA Chimica

基　　金：国家自然科学基金(编号:21901011)资助项目。

摘　　要：平面型N/O四配位钴配合物参与的自由基反应研究近年来取得了许多新进展,双水杨醛缩乙二胺类(Salen)钴配合物作为其中重要的代表,在小分子和高分子合成中展现出丰富全面的反应性质.本文总结了近10年来这一领域的重要进展,包括以下方面:(1)基于氢原子转移的Co(Ⅱ/Ⅲ)催化反应;(2)基于Co(Ⅳ)的氧化型氢官能团化反应;(3)基于Co(Ⅲ)卡宾自由基的环丙烷化反应;(4)基于Co(Ⅰ)的还原偶联反应;(5) Co介导的自由基聚合,并重点介绍这些反应之间的机理联系、新型催化模式的发展以及合成应用.Studies on the radical reactions involving planar N/O four-coordinated cobalt complexes have recently made significant progress. Cobalt salen(N,N′-bis(salicylidene)ethylenediamine) complexes, being one of the most important members of this family, have demonstrated outstanding versatility in the synthesis of small molecules as well as polymers. Herein we summarize important new advances in this field over the past 10 years, including:(1) Co(Ⅱ/Ⅲ)catalysis via hydrogen atom transfer;(2) oxidative hydrofunctionalization reactions involving Co(Ⅳ);(3)cyclopropanation via Co(Ⅲ) carbene radicals;(4) reductive couplings via Co(Ⅰ);(5) cobalt-mediated radical polymerizations. Emphasis is placed on the mechanistic interconnections among various reactions, development of new catalysis modes, and synthetic applications.

关 键 词：自由基 钴催化 SALEN 氢原子转移 活性聚合 

分 类 号：O621.251[理学—有机化学] O641.4[理学—化学]