By employing an acceptorless BH/NH dehydrocoupling strategy, regioselective B(3)-amination of o-carboranes with amines has been achieved via iridium catalysis, offering an array of B(3)-aminated-o-carboranes in one-pot process.

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.