Reversing Conventional Site-Selectivity:Electrochemically Driven C(sp^(2))-H/C(sp^(3))-H Coupling with H_(2)Evolution

作     者：Xuelian Zheng Pan Peng Cheng Huang Qingquan Lu Xuelian Zheng;Pan Peng;Cheng Huang;Qingquan Lu

作者机构：The Institute for Advanced StudiesWuhan UniversityWuhan 430072 

出 版 物：《CCS Chemistry》 (中国化学会会刊（英文）)

年 卷 期：2023年第5卷第5期

页      面：1086-1095页

核心收录：

学科分类：07[理学] 070303[理学-有机化学] 0703[理学-化学] 

基　　金：support from the“1000-Youth Talents Plan”(Prof.Q.L.)and Wuhan University are greatly appreciated. 

主　　题：electrosynthesis electrooxidation C–H functionalization oxidative coupling alkylation 

摘      要：Sustainable and site-selective C–H functionalization is still a challenge because of the comparable properties of bonds of the same type.Here,an electrochemical C(sp^(2))–H/C(sp^(3))–H coupling with aryl iodides is reported for the first time.The C(sp^(2))–H bond outperformed the much weaker C(sp^(2))–I bond participating in C(sp^(2))–H/C(sp^(3))–H coupling.This protocol features mild reaction conditions,good functional group tolerance,and scalability.Crosscoupling products with C–I bonds are versatile moieties for further synthetic manipulation,that can undergo Suzuki,Sonogashira,Ullmann-Ma,Catellani,Heck reactions,and so on to introduce new functional groups into target molecules with good yields.Mechanistic investigations showed that the site selectivity of the reaction is enabled by an iodineassisted[3,3]-sigmatropic rearrangement,and the interaction of hypervalent iodine generated in situ with an enolate is the rate-determining step.