有机化学 ›› 2020, Vol. 40 ›› Issue (11): 3686-3696.DOI: 10.6023/cjoc202006008 上一篇    下一篇

所属专题: 创刊四十周年专辑

综述与进展

仿生金属配合物催化的C(sp3)—H键不对称氧化反应研究进展

孙强盛, 孙伟   

  1. 中国科学院兰州化学物理研究所 羰基合成与选择氧化国家重点实验室 分子合成科学卓越创新中心 兰州 730000
  • 收稿日期:2020-06-05 修回日期:2020-06-19 发布日期:2020-07-09
  • 通讯作者: 孙伟 E-mail:wsun@licp.cas.cn
  • 基金资助:
    国家自然科学基金(Nos.21773273,21473226,21902166)、中国科学院前沿科学重点研究计划(No.QYZDJ-SSW-SLH051)和江苏省自然科学基金青年基金(No.BK20170420)资助项目.

Recent Progress in C(sp3)-H Asymmetric Oxidation Catalyzed by Bioinspired Metal Complexes

Sun Qiangsheng, Sun Wei   

  1. State Key Laboratory for Oxo Synthesis and Selective Oxidation, Center for Excellence in Molecular Synthesis, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000
  • Received:2020-06-05 Revised:2020-06-19 Published:2020-07-09
  • Supported by:
    Project supported by the National Natural Science Foundation of China (Nos. 21773273, 21473226, 21902166), the Key Research Program of Frontier Sciences, CAS (No. QYZDJ-SSW-SLH051) and the Natural Science Foundation of Jiangsu Province (No. BK20170420).

C—H氧化反应是一类重要的有机反应,其中C—H不对称氧化反应可以将简单烃类化合物直接转化为手性醇和酮等,为复杂分子的合成提供了更加经济和高效的方法.尽管在过去的数十年,很多化学家致力于不对称C—H氧化反应研究,但由于C—H键本身的惰性和C—H键之间微弱的立体性差异,该研究领域的进展依然缓慢.结合影响C—H氧化反应的因素、生物酶催化氧化机制与仿生金属配合物催化剂的发展,从配体类型的角度阐述当前所实现的C—H键不对称氧化的一些反应实例.

关键词: C—H氧化, 金属配合物, 不对称氧化

C—H oxidation represents one of the most important reactions in organic chemistry. In particular, asymmetric C—H oxidation, which can directly convert simple alkanes into chiral alcohols, ketones, aldehydes and so on, provides more economic and efficient access to the synthesis of complex molecules. Although increasing efforts have been devoted to this area, asymmetric C—H oxidation is still far away from the goal due to the inert nature of C—H and the subtle stereo-difference of C—H bonds. The factors that dictate the selectivity of asymmetric C—H oxidation, mechanism of the C—H oxidation catalyzed by enzyme and some successful examples achieved by biomimetic metal complexes bearing various ligands are reviewed.

Key words: C-H oxidation, metal complex, asymmetric oxidation