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...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.展开更多
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。
文摘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.
