有机化学 ›› 2017, Vol. 37 ›› Issue (5): 1117-1126.DOI: 10.6023/cjoc201702020 上一篇    下一篇

所属专题: 热点论文合辑

综述与进展

过渡金属催化重氮化合物参与的芳烃碳(sp2)-氢键官能团化研究进展

刘路, 张俊良   

  1. 华东师范大学化学与分子工程学院 上海市绿色化学与化工过程绿色化重点实验室 上海 200241
  • 收稿日期:2017-02-16 修回日期:2017-03-10 发布日期:2017-03-14
  • 通讯作者: 刘路 E-mail:lliu@chem.ecnu.edu.cn
  • 基金资助:

    上海市浦江人才计划(No.14PJ1403100)、科技部国家重点基础研究计划(973计划,No.2015CB856600)、国家自然科学基金(Nos.21372084,21425205,21572065)和长江学者与创新团队发展计划资助项目.

Development of Transition-Metal-Catalyzed C(sp2)-H Functionalization of Arenes with Diazo Compounds

Liu Lu, Zhang Junliang   

  1. Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200241
  • Received:2017-02-16 Revised:2017-03-10 Published:2017-03-14
  • Contact: 10.6023/cjoc201702020 E-mail:lliu@chem.ecnu.edu.cn
  • Supported by:

    Project supported by the Shanghai Pujiang Program (No. 14PJ1403100), the National Basic Research Program of China (973 Program, No. 2015CB856600), the National Natural Science Foundation of China (Nos. 21372084, 21425205, 21572065), and the Changjiang Scholars and Innovative Research Team in University.

碳-氢键官能团化已经成为化学中最重要的研究课题之一.控制碳-氢键官能团化的区域选择性在目前是最关键的问题,同时也很具有挑战性.过渡金属催化的重氮化合物的有机转化,例如杂-氢键插入、环丙烷化、交叉偶联反应以及烷基碳-氢[C(sp3)-H]键官能化反应发展比较成熟,但是芳烃的碳-氢[C(sp2)-H]键官能团化反应研究较少.这篇综述总结了过渡金属催化重氮化合物参与的芳烃的碳-氢[C(sp2)-H]键官能团化反应研究进展.为了实现反应的选择性,有两种策略运用在其中.一种是导向的碳-氢(C-H)键活化,主要得到邻位碳-氢键官能团化产物;另外一种是非导向策略,主要表现出对位选择性.对一些代表性的例子也做了机理介绍.

关键词: 过渡金属催化, 重氮化合物, 芳烃, 碳-氢键官能团化, 区域选择性

C-H bond functionalization has been one of the most important subject in chemistry. How to control the site selectivity of C-H bond is the key issue and remain challenge. Transition-metal-catalyzed organic tranformation of diazo compounds, such as X-H (X=O, N, S, etc.) insertion, cyclopropanation, cross-coupling reactions and C(sp3)-H functionalization, have been well established, whereas the C(sp2)-H functionalization using diazo compounds is less developed. This review will summarize the progress in transition-metal-catalyzed C(sp2)-H functionalization of arenes with diazo compounds. To realize the site selectivity, two strategies are utilized. One is directed C-H activation, which gives the ortho-selective C-H functionalization products. The other is undirected approach, which normally exhibits para-selectivity. In order to understand these reactions, the mechanisms for selected examples are also provided.

Key words: tansition-metal-catalysis, diazo compound, arene, C-H bond functionalization, site selective