Rh(III)-Catalyzed Enantioselective Multicomponent C−H Functionalization Cascade toward Chiral Indoles

Abstract The development of catalytic strategies that transform simple substrates into complex chiral architectures in a single operation is a longstanding goal in synthetic chemistry. Here, we report a Rh(III)-catalyzed enantioselective multicomponent C−H functionalization that provides direct access to valuable chiral (indol-2-yl)methanamines from readily available indoles, alkenes, and aminating agents. Orchestrated by a chiral Rh(III) catalyst, this cascade integrates indole C2−H activation, alkene chain walking, and enantioselective C−N bond formation to accomplish a rare 1,1-carboamination manifold, delivering enantioenriched indoles with high efficiency and enantiocontrol (up to 80% yield, 99% ee). This study highlights the potential of enantioselective multicomponent C−H functionalization as a versatile and efficient platform for the rapid assembly of value-added chiral architectures.