有机化学 ›› 2021, Vol. 41 ›› Issue (11): 4409-4414.DOI: 10.6023/cjoc202104028 上一篇    下一篇

研究论文

钴(II)-三联吡啶配位聚合物催化的苄位直接氧化

刘建奇, 范伟伟*(), 熊航行, 江京耘, 詹红菊   

  1. 荆楚理工学院化工与药学院 湖北荆门 448000
  • 收稿日期:2021-04-14 修回日期:2021-06-10 发布日期:2021-08-09
  • 通讯作者: 范伟伟
  • 基金资助:
    湖北省科技创新群体项目(T2020023); 荆门市科技计划(2020ZDYF002)

Benzylic Oxidation Catalyzed by Cobalt(II)-Terpyridine Coordination Polymers

Jianqi Liu, Weiwei Fan(), Hangxing Xiong, Jingyun Jiang, Hongju Zhan   

  1. College of Chemical Engineering and Pharmacy, Jingchu University of Technology, Jingmen, Hubei 448000
  • Received:2021-04-14 Revised:2021-06-10 Published:2021-08-09
  • Contact: Weiwei Fan
  • Supported by:
    Hubei Provincial Scientific and Technological Innovation Team Project(T2020023); Science and Technology Plan Project of Jingmen City(2020ZDYF002)

通过苄位C—H直接氧化制备了一系列芳香酮类化合物. 该反应体系采用钴(II)-三联吡啶配位聚合物作为催化剂, 叔丁基过氧化氢(TBHP)作为氧化剂, Na2CO3作为助催化剂, 水作为溶剂, 以较高的收率(78%~99%)制得了19种芳香酮类化合物. 该方法底物适用范围广, 具有较高的化学选择性和官能团耐受性. 通过2,2,6,6-四甲基哌啶-1-氧(TEMPO)的自由基捕获实验及对反应过程中中间体的监测, 提出了一种合理的自由基反应机理.

关键词: 苄位直接氧化, 配位聚合物, 叔丁基过氧化氢, 酮类

Direct benzylic C—H oxidation for the synthesis of aromatic ketones was developed. Employing cobalt(II)-terpyridine coordination polymers as catalyst, tert-butyl hydroperoxide (TBHP) as oxidant and Na2CO3 as activator, 19 aromatic ketones were prepared with good to excellent yields (78%~99%) in water. The reaction showed a broad range of substrates with good functional group tolerance and chemical selectivity. By control experiments, a trapping experiment using 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) and detection of intermediates during reaction, a reasonable radical mechanism for this type of reaction was also demonstrated.

Key words: direct benzylic oxidation, coordination polymer, tert-butyl hydroperoxide, ketone