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

doi:10.6023/cjoc202005080

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

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^a, 王杨阳^a, 杨金月^a, 吴高荣^a, 夏成才^b, 冀亚飞^a

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 E-mail:xiachc@163.com;jyf@ecust.edu.cn
基金资助:
国家自然科学基金（No.21676088）资助项目.

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

Fu Xiaopan^a, Wang Yangyang^a, Yang Jinyue^a, Wu Gaorong^a, Xia Chengcai^b, Ji Yafei^a

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).

1. cjoc202005080.pdf(7245KB)

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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Fu Xiaopan, Wang Yangyang, Yang Jinyue, Wu Gaorong, Xia Chengcai, Ji Yafei. Fully Substituted Pyrazoles Assisted Palladium-Catalyzed Late-Stage Arylation of C(sp²)—H Bond[J]. Chinese Journal of Organic Chemistry, 2020, 40(12): 4305-4314.

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钯催化全取代吡唑导向的C(sp²)—H键后期芳基化反应

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

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钯催化全取代吡唑导向的C(sp2)—H键后期芳基化反应