Chinese Journal of Organic Chemistry ›› 2020, Vol. 40 ›› Issue (12): 4305-4314.DOI: 10.6023/cjoc202005080 Previous Articles     Next Articles


付小盼a, 王杨阳a, 杨金月a, 吴高荣a, 夏成才b, 冀亚飞a   

  1. a 华东理工大学药学院 制药工程与过程化学教育部研究中心 上海 200237;
    b 山东第一医科大学(山东省医学科学院)药学院 山东泰安 271016
  • 收稿日期:2020-05-28 修回日期:2020-06-28 发布日期:2020-07-23
  • 通讯作者: 夏成才, 冀亚飞;
  • 基金资助:

Fully Substituted Pyrazoles Assisted Palladium-Catalyzed Late-Stage Arylation of C(sp2)—H Bond

Fu Xiaopana, Wang Yangyanga, Yang Jinyuea, Wu Gaoronga, Xia Chengcaib, Ji Yafeia   

  1. a Engineering Research Centre of Pharmaceutical Process Chemistry, Ministry of Education, School of Pharmacy, East China University of Science & Technology, Shanghai 200237;
    b Pharmacy College, Shandong First Medical University & Shandong Academy of Medical Sciences, Taian, Shandong 271016
  • Received:2020-05-28 Revised:2020-06-28 Published:2020-07-23
  • Supported by:
    Project supported by the National Natural Science Foundation of China (No. 21676088).

A successful protocol has been developed for palladium-catalyzed late-stage arylation of fully substituted pyrazoles. Through screening of optimazation of reaction parameters, the most efficient reaction conditions for mono-ortho-position arylation were obtained. This reaction features a broad substrate scope, good functional group tolerance as well as good to excellent yield. Moreover, the intermolecular competition experiments and gram scale reaction were also performed. The kinetic isotopic effect (KIE) result reveled C-H bond cleavage was involved in the rate-limiting step and a plausible mechanism was proposed based on the dual-core dimeric palladacycle.

Key words: mono-arylation, late-stage functionalization, fully substituted pyrazole, C(sp2)-H bond