Rh-Catalyzed Intermolecular Carbenoid Functionalization of Aromatic C–H Bonds by α-Diazomalonates

A Rh-catalyzed intermolecular coupling of diazomalonates with arene C-H bonds is reported. The reaction is initiated by electrophilic C-H activation, which is followed by coupling of the arylrhodium(III) complex with the diazomalonate. In most cases, arenes with oximes, carboxylic acids, and amines as directing groups cross-couple with diazomalonates with excellent regioselectivities and functional group tolerance, and thus, this reaction offers a new route to α-aryl carbonyl compounds for specific applications.