有机化学 ›› 2015, Vol. 35 ›› Issue (4): 781-788.DOI: 10.6023/cjoc201409046 上一篇    下一篇

综述与进展

导向的过渡金属催化不活泼C(sp3)—H键氧化反应研究进展

谭明雄a,b, 顾运琼a,b, 罗旭健a, 张培a   

  1. a 玉林师范学院化学与材料学院 玉林 537000;
    b 广西师范大学药用资源化学与药物分子工程教育部重点实验室 桂林 541004
  • 收稿日期:2014-10-03 修回日期:2014-10-05 发布日期:2014-12-08
  • 通讯作者: 谭明雄 E-mail:mxtan5a@yahoo.com
  • 基金资助:

    国家自然科学基金(No. 21261025)、药用资源化学与药物分子工程教育部重点实验室开放基金(Nos. CMEMR2011-09, CMEMR2014-B08)、广西高校高水平创新团队及卓越学者计划.

Progress in Directed Transition Metal-Catalyzed Oxidation of Inactive C(sp3)—H Bonds

Tan Mingxionga,b, Gu Yunqionga,b, Luo Xujiana, Zhang Peia   

  1. a College of Chemistry and Materials, Yulin Normal University, Yulin 537000;
    b Key Laboratory for the Chemistry and Molecular Engineering of Medicinal Resources, Guangxi Normal University, Guilin 541004
  • Received:2014-10-03 Revised:2014-10-05 Published:2014-12-08
  • Supported by:

    Project supported by the National Natural Science Foundation of China (No. 21261025), the Key Laboratory for the Chemistry and Molecular Engineering of Medicinal Resources, Ministry of Education (Nos. CMEMR2011-09, CMEMR2014-B08), and the Innovative Team & Outstanding Talent Program of Colleges and Universities in Guangxi.

近年来, 过渡金属催化不活泼C(sp3)—H键氧化反应取得重要进展. 该领域的研究主要集中在过渡金属催化甲烷选择性氧化, 以及过渡金属催化导向基团螯合甲基氧化方面, 这些研究成果实现了许多传统氧化方法不能完成的高效选择性转化. 重点概述导向基团(肟、噁唑啉、吡啶、酰胺、羧酸、羟基)对促进过渡金属催化氧化C(sp3)—H键的影响, 底物的乙酰氧基化、羟基化、羰基化、酯化反应以及催化反应体系和相关机制.

关键词: 过渡金属催化, 不活泼C(sp3)—H键, 氧化反应

The recent progress in transition metal-catalyzed oxidation of C(sp3)—H bonds has been made. Researches focus on the selective oxidation of methane, as well as the oxidation of methyl groups assisted by chelating directing groups. The researches lead to efficient and highly selective oxidative conversion that are unable to solve by traditional methods. This review covers the effect of directing groups (oxime, oxazoline, pyridine, amide, carboxylic acid, and hydroxyl) on promoting oxidation of C(sp3)—H bonds, the formation of acetylation, hydroxylation, carbonylation, esterification, and metal-catalyzed oxidative reaction system and mechanisms.

Key words: transition metal-catalyzed, inactive C(sp3)—H bonds, oxidation