Ir‐Catalyzed B(3)‐Amination of o‐Carboranes with Amines via Acceptorless Dehydrogenative BH/NH Cross‐Coupling

Abstract

An efficient and convenient strategy for Ir‐catalyzed selective B(3)‐amination of o‐carboranes with amines via acceptorless BH/NH dehydrocoupling was developed, affording a series of B(3)‐aminated‐o‐carboranes in moderate to high isolated yields with H2 gas as a sole by‐product. Such an oxidant‐free system endues the protocol sustainability, atom‐economy and environmental friendliness. A reaction mechanism via an Ir(I)‐Ir(III)‐Ir(I) catalytic cycle involving oxidative addition, dehydrogenation and reductive elimination was proposed.