有机化学    下一篇

综述与进展

光氧化还原催化下以肟的衍生物作为前体亚胺自由基的产生及其反应

宋常华a,b, 沈许b, 于芳a, 何宇鹏a, 俞寿云b   

  1. a 辽宁石油化工大学 化学化工与环境学部 抚顺 113001;
    b 南京大学化学化工学院 生命分析化学国家重点实验室 南京 210023
  • 收稿日期:2020-04-06 修回日期:2020-04-29 出版日期:2030-01-01 发布日期:2020-05-08
  • 通讯作者: 俞寿云, 何宇鹏 E-mail:yushouyun@nju.edu.cn;yupeng.he@lnpu.edu.cn
  • 基金资助:
    项目受国家自然科学基金重点项目(Nos.21732003和21978124)和辽宁省省教育厅高等学校创新人才项目资助(No.LR2018019).

Generation and Application of Iminyl Radicals from Oxime Derivatives Enabled by Visible Light Photoredox Catalysis

Changhua Songa,b, Xu Shenb, Fang Yua, Yu-Peng Hea, Shouyun Yub   

  1. a College of Chemistry, Chemical Engineering and Environmental Engineering, Liaoning Shihua University, Fushun 113001;
    b State Key Laboratory of Analytical Chemistry for Life Science, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023
  • Received:2020-04-06 Revised:2020-04-29 Online:2030-01-01 Published:2020-05-08
  • Supported by:
    Project supported by the National Natural Science Foundation of China (Nos. 21732003 and 21978124) and Innovative Talent Project of Educational Department of Liaoning Provincial (No. LR2018019).

在可见光氧化还原催化的条件下,可以从肟的衍生物(O-酰基肟、O-芳基肟和a-亚胺氧杂酸等)高效清洁的产生亚胺自由基。该产生方法促进了亚胺自由基反应活性的系统研究。亚胺自由基主要有以下四种反应模式:(1)对芳烃的加成反应;(2)分子内的氢迁移;(3)对烯烃的加成反应;(4)Norrish-I型断裂(a-位的碳-碳键断裂)反应。本文综述了近几年来在光氧化还原催化的条件下以肟的衍生物作为前体,亚胺自由基的产生及其参与的典型反应。

关键词: 氮自由基, 亚胺自由基, 光氧化还原催化, 可见光

The advent of visible light photoredox catalysis has transformed the way of single-electron transfer (SET) processes and access radical species. As a result, the chemistry of nitrogen-centered radicals has witnessed a remarkable gain in interest. Specifically, under visible light photoredox catalysis, iminyl radicals can be generated from oxime derivatives, such as O-acyl oximes, O-aryl oximes and a-imino-oxy acids. Meanwhile, the reactivity of iminyl radcials is investigated systematically. Iminyl radicals can undergo four major classes of reactions, namely 1) addition to arenes, 2) intramolecular hydrogen atom transfer and subsequent reactions, 3) addition to alkenes, 4) Norrish type-I fragmentation (cleavage of a-carbon-carbon bonds) and subsequent reactions. In this REVIEW article, we discuss the most significant progresses in the use of oximes and their derivatives as iminyl precursors and outline their engagement in photoredox-mediated transformations.

Key words: nitrogen-centered radical, iminyl radical, photoredox catalysis, visible light