Rhodium(III)-Catalyzed B(4)-Azo Coupling of o-Carboranes with Aryl Diazonium Tetrafluoroborates

Rh(III)-catalyzed B(4)-azo coupling reactions of o-carborane acids with aryl diazonium tetrafluoroborates have been developed, leading to the regioselective formation of B(4)-azo-coupled o-carboranes. Moreover, B(4)-azo-coupled o-carboranes can be further functionalized by introducing a second azo group, producing B(4)–C(1)-di(arylazo) o-carborane. The B(4)-azo group as an efficient directing group enables catalytic C–H amidation reactions, providing a new synthetic route for complex o-carborane derivatives.