Regiocontrolled Rh(Ⅲ)-catalyzed C-C coupling/C-N cyclization mediated by distinctive 1,2-migratory insertion of gem-difluoromethylene allenes:Reaction development and mechanistic insight  

作　　者：Zhi Zhou Kaifeng Chen Yi Wang Xiuhua Zhong Shuang Lin Hui Gao Wei Yi 

机构地区：[1]Guangzhou Municipal and Guangdong Provincial Key Laboratory of Molecular Target&Clinical Pharmacology,NMPA and State Key Laboratory of Respiratory Disease,School of Pharmaceutical Sciences and the Fifth Affiliated Hospital,Guangzhou Medical University,Guangzhou 511436,China

出　　处：《Chinese Chemical Letters》2023年第5期250-255,共6页中国化学快报（英文版）

基　　金：the National Natural Science Foundation of China(NSFC,Nos.21877020,22007020);Natural Science Foundation of Guangdong Province(No.2019A1515010935);Science and Technology Program of Guangzhou(No.202102020615)for financial support on this study。

摘　　要：By developing gem-difluoromethylene allenes as viable partners,regiocontrolled Rh(Ⅲ)-catalyzed redoxneutral C-C coupling/C-N cyclization has been realized to build the pyridin-2(1H)-one motifs with the embedment of a Z-configured monofluoroalkene functionality,in which either(hetero)aromatic or vinylic amides were found to be compatible.Integrated experimental and computational mechanistic studies revealed that a tandem regioselective allene 1,2-insertion/β-H elimination/hydrogen transfer/oxidative addition/cyclization/cis-β-F elimination involving an unconventional Rh(Ⅲ)-Rh(I)-Rh(Ⅲ)catalytic cycle accounts for the established transformation.Through further FMO analysis and IGMH maps,a non-covalent weak interaction network between the gem-difluoromethylene part and the OPiv moiety was rationally defined for the unconventional and specific regioselectivity control.

关 键 词：Gem-difluoromethylene allenes C-H functionalization REGIOCONTROL Rhodium(Ⅲ)catalysis DFT calculations 

分 类 号：O621.251[理学—有机化学]