文献类型：期刊文献

中文题名：钯催化全取代吡唑导向的C(sp^2)—H键后期芳基化反应

英文题名：Fully Substituted Pyrazoles Assisted Palladium-Catalyzed Late-Stage Arylation of C(sp^2)-H Bond

作者：付小盼[1];王杨阳[1];杨金月[1];吴高荣[1];夏成才[2];冀亚飞[1]

机构：[1]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;[2]山东第一医科大学(山东省医学科学院)药学院,山东泰安271016

年份：2020

卷号：40

期号：12

起止页码：4305

中文期刊名：有机化学

外文期刊名：Chinese Journal of Organic Chemistry

收录：CSTPCD;;Scopus;WOS:【SCI-EXPANDED(收录号:WOS:000611068200025)】；北大核心:【北大核心2017】；CSCD:【CSCD2019_2020】；

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

语种：中文

中文关键词：芳基化;后期官能化;全取代的吡唑;C(sp^2)—H键;

外文关键词：mono-arylation;late-stage functionalization;fully substituted pyrazole;C(sp2)—H bond;

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.
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-orthoposition 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.