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 

机构地区：[1]The Institute for Advanced Studies,Wuhan University,Wuhan 430072

出　　处：《CCS Chemistry》2023年第5期1086-1095,共10页中国化学会会刊（英文）

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

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.

关 键 词：ELECTROSYNTHESIS ELECTROOXIDATION C–H functionalization oxidative coupling ALKYLATION 

分 类 号：O62[理学—有机化学]