Rhodium-Catalyzed Amidation of the Cage B(4)–H Bond in o‑Carboranes with Dioxazolones by Carboxylic Acid-Assisted B(4)–H Bond Activation

A rhodium-catalyzed direct and regioselective amidation of the cage B(4)–H bond in a wide range of o-carboranes with alkyl-, aryl-, and heteroaryl-substituted dioxazolones is demonstrated by carboxylic acid-assisted B(4)–H bond activation in carborane clusters, providing a number of amidated o-carboranes in high yields with the release of carbon dioxide. Moreover, the selective 2-fold decarboxylative amidation reaction of the cage B(4)–H bond in o-carborane was accessed.