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.

  • 单位
    呼吸疾病国家重点实验室