Rh(III)-Catalyzed Divergent Ring Remodeling of Oxindole with Diazo Compounds via Amide and C–H Bond Activation

An efficient and versatile Rh(III)-catalyzed divergent ring-remodeling strategy that transforms readily accessible oxindoles using suitable diazo compounds into highly substituted indoles and unsymmetrically 2,6-dialkylated anilines via amide bond activation and subsequent C–H bond activation is reported. This unified platform enables rapid scaffold diversification, including effective late-stage modification of complex substrates. Mechanistic investigations, supported by control experiments, indicate a pathway involving Rh(III)-catalyzed oxindole solvolysis, formation of cyclometalated species, metal–carbene formation, migratory insertion, protodemetalation, and final intramolecular dehydration of the resulting enol–amine intermediates.