TEMPO-Regulated Regio-and Stereoselective Cross-Dihalogenation with Dual Electrophilic X^(+) Reagents

作     者：Yi Kong Tongxiang Cao Shifa Zhu Yi Kong;Tongxiang Cao;Shifa Zhu

作者机构：Key Laboratory of Functional Molecular Engineering of Guangdong ProvinceSchool of Chemistry and Chemical EngineeringSouth China University of TechnologyGuangzhouGuangdong510640 China 

出 版 物：《Chinese Journal of Chemistry》 (中国化学（英文版）)

年 卷 期：2021年第39卷第11期

页      面：3004-3010页

核心收录：

学科分类：081704[工学-应用化学] 07[理学] 08[工学] 0817[工学-化学工程与技术] 070303[理学-有机化学] 0703[理学-化学] 

基　　金：financial support from the NSFC(Nos.21871096,22071062,22001077) the Ministry of Science and Technology of the People’s Republic of China(No.2016YFA0602900) the Guangdong Science and Technology Department(Nos.2018B030308007,2021A1515012331) the China Postdoctoral Science Foundation(Nos.2018M643062,2019T120723) 

主　　题：Halogenation Organocatalysis Electrophilic addition Redox-regulation Alkynes 

摘      要：A TEMPO catalyzed cross-dihalogenation reaction was established via redox-regulation of the otherwise complex system of dual electrophilic X+***,the ICl,BrCl,I_(2) and Br_(2) were generated in-situ,which enabled high regio-or stereoselective access to a myriad of iodochlorination,bromochlorination and homo-dihalogenation products with a wide spectrum of *** its mild conditions and operational simplicity,this method could enable wide applications in organic synthesis,which was exemplified by divergent synthesis of two *** mechanistic investigations via radical clock reaction,pinacol ring expansion and Hammett experiments were conducted,which confirmed the intermediacy of halonium *** addition,a dynamic catalytic model based on the versatile catalytic role of TEMPO was proposed to explain the selective outcomes.