化学学报 ›› 2017, Vol. 75 ›› Issue (1): 22-33.DOI: 10.6023/A16080418 上一篇    下一篇

所属专题: 有机光化学

研究展望

催化不对称光诱导自由基反应

王德红a,b, 张龙a,b, 罗三中a,b   

  1. a 中国科学院化学研究所 分子识别与功能院重点实验室 北京 100190;
    b 中国科学院大学 北京 100049
  • 投稿日期:2016-08-16 修回日期:2016-09-13 发布日期:2016-09-18
  • 通讯作者: 罗三中,E-mail:luosz@iccas.ac.cn;Tel.:0086-010-62554446 E-mail:luosz@iccas.ac.cn
  • 作者简介:王德红:中国科学院化学研究所2013级在读硕博生,本科就读于东北师范大学.现在主要研究光催化和伯胺催化的不对称转化反应;张龙:中国科学院化学研究所分子识别与功能重点实验室副研究员.主要从事不对称光催化、仿生伯胺催化及其理论计算研究;罗三中:中国科学院化学研究所研究员、博士生导师,分子识别与功能重点实验室副主任.主要从事仿生小分子催化合成和物理有机研究.
  • 基金资助:

    项目受国家自然科学基金(Nos.21572232,21390400)资助.

Photo-induced Catalytic Asymmetric Free Radical Reactions

Wang Dehonga,b, Zhang Longa,b, Luo Sanzhonga,b   

  1. a Key Laboratory of Molecular Recognition and Functions, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190;
    b University of Chinese Academy of Sciences, Beijing 100049
  • Received:2016-08-16 Revised:2016-09-13 Published:2016-09-18
  • Supported by:

    Project supported by the National Natural Science Foundation of China (Nos. 21572232, 21390400).

自由基反应的立体选择性调控一直是不对称催化领域的挑战性难题.近年来,光化学过程特别是可见光化学过程在有机合成中越来越受到研究人员的重视,光诱导自由基化学也再次进入人们的视野.相对传统的自由基化学,光诱导自由基化学反应条件温和,易于调控,为实现高效催化不对称自由基反应带来了新的契机,展示了蓬勃的发展潜力.本文根据光诱导产生自由基种类的不同,简要介绍最近该方向的研究进展.

关键词: 光诱导, 自由基反应, 不对称催化, 协同催化

Enantioselective control of free radical reactions has eluded organic chemists for decades. Echoed with the renaissance of photo-induced processes, or so called photocatalysis or photoredox catalysis in organic synthesis, photo-induced organic radical chemistry has regained its prominence in developing catalytic asymmetric radical reaction. The generally mild conditions inherited with photochemistry, particularly visible light photo-processes, have allowed for controllable generation of free radicals as well as the subsequent bond formations. The past five years have witnessed dramatic advances in exploring photo-induced catalytic asymmetric free radical reactions, and enormous potentials along this line are envisaged. This perspective gives a brief summary on the important advances in this field. Accordingly, the major advances are classified based on different radical species including α-amino/oxyl radicals, radicals generated from enones and its analogues, benzyl radicals, α-carbonyl radicals, polyhalogenated alkyl radicals and nitrogen radicals. Brief discussion of mechanism is presented whenever relevant.

Key words: photoredox catalysis, free radical reaction, asymmetric catalysis, synergistic catalysis