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2020 , Vol. 40 >Issue 12: 4305 - 4314

DOI: https://doi.org/10.6023/cjoc202005080

研究论文

钯催化全取代吡唑导向的C(sp2)—H键后期芳基化反应

  • 付小盼 ,
  • 王杨阳 ,
  • 杨金月 ,
  • 吴高荣 ,
  • 夏成才 ,
  • 冀亚飞
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  • 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

  网络出版日期: 2020-07-23

基金资助

国家自然科学基金（No.21676088）资助项目.

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

  • Fu Xiaopan ,
  • Wang Yangyang ,
  • Yang Jinyue ,
  • Wu Gaorong ,
  • Xia Chengcai ,
  • Ji Yafei
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  • 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 date: 2020-05-28

  Revised date: 2020-06-28

  Online published: 2020-07-23

Supported by

Project supported by the National Natural Science Foundation of China (No. 21676088).

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摘要

发展了一种钯催化全取代吡唑类化合物的邻位C（sp2）—H键后期芳基化的反应体系.通过对反应条件的优化，得到了最高效的芳基化反应条件.该催化体系表现出广泛的底物适用性、良好的官能团耐受性以及优良的分离收率.进行了控制实验，如分子间的竞争实验和放大克级实验，氘代动力学实验证明了C-H键的断裂是决速步骤.最后，通过制备双核二聚体环钯化中间体，提出了合理的钯催化循环反应机理.

关键词： 芳基化; 后期官能化; 全取代的吡唑; C (sp2)—H键

本文引用格式

付小盼 , 王杨阳 , 杨金月 , 吴高荣 , 夏成才 , 冀亚飞 . 钯催化全取代吡唑导向的C(sp2)—H键后期芳基化反应[J]. 有机化学, 2020 , 40(12) : 4305 -4314 . DOI: 10.6023/cjoc202005080

Abstract

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

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