有机化学 ›› 2020, Vol. 40 ›› Issue (1): 133-139.DOI: 10.6023/cjoc201907002 上一篇    下一篇

研究论文

可见光促进三级胺α位C(sp3)—H键的胺化反应研究

赵亚婷a,b, 曾俊杰b, 夏吾炯b   

  1. a 衢州学院化学与材料工程学院 浙江衢州 324000;
    b 哈尔滨工业大学(深圳)城市水资源与水环境国家重点实验室 广东深圳 518055
  • 收稿日期:2019-07-02 修回日期:2019-08-20 出版日期:2020-01-25 发布日期:2019-09-05
  • 通讯作者: 赵亚婷, 夏吾炯 E-mail:liveagain@126.com;xiawj@hit.edu.cn
  • 基金资助:
    国家自然科学基金(Nos.21901141,21672047)和衢州学院科研启动基金(No.BSYJ201714)资助项目.

Visible-Light-Induced α-C(sp3)—H Amination Reactions of Tertiary Amines

Zhao Yatinga,b, Zeng Junjieb, Xia Wujiongb   

  1. a College of Chemical and Material Engineering, Quzhou University, Quzhou, Zhejiang 324000;
    b State Key Laboratory of Urban Water Resource and Environment, School of Science, Harbin Institute of Technology[Shenzhen], Shenzhen, Guangdong 518055
  • Received:2019-07-02 Revised:2019-08-20 Online:2020-01-25 Published:2019-09-05
  • Supported by:
    Project supported by the National Natural Science Foundation of China (Nos. 21901141, 21672047), and the Start-up Funds of Quzhou University (No. BSYJ201714).

报道了可见光催化氧化还原循环促进三级胺α位C(sp3)—H键的胺化反应.该反应使用简单、易得的N-苯甲酰氧基邻苯二甲酰亚胺为氨基自由基前体,利用廉价、可再生的可见光作为绿色能源,首次实现了一系列NN-二甲基苯胺衍生物的α位C(sp3)—H键的直接胺化.该方法涉及双自由基交叉偶联机理,具有条件温和、收率与官能团兼容性良好以及底物适用范围广的特点,为三级胺类化合物的官能团修饰提供了一种简单、安全、便利的新途径.

关键词: 光催化氧化还原循环, 氮自由基, 胺化反应, C—H官能团化, 自由基偶联

Herein, the visible-light-induced α-C(sp3)—H amination reactions of tertiary amines were reported. By using readily available 1,3-dioxoisoindolin-2-yl benzoate as precursor of N-radical and blue LEDs as green and sustainable energy source, the α-C(sp3)—H bonds of various N,N-dimethylaniline derivatives were aminated directly. Based on radical trapping experiment and documented literature, a mechanism involving radicals coupling was proposed. This method featured in mild reaction conditions and good functional group tolerance, which provides a simple and practical protocol to the modification of tertiary amines.

Key words: photoredox catalysis, N-radical, amination reaction, C—H functionalization, radicals coupling