Ir-Catalyzed –COOH directed site-selective B–H/C–H dehydrogenative cross-coupling of o-carborane with thiophenes has been achieved for the first time. Without any pre-functionalization, carboranyl carboxylic acids and thiophenes can serve as suitable coupling partners, resulting in the preparation of 4-thienyl-o-carboranes in a simple one-pot process for potential applications in materials.

Transition metal catalyzed regioselective amination of the cage B(4)–H bond in o-carboranes has been achieved for the first time using O-benzoyl hydroxylamines or organic azides as the amination reagents, leading to the preparation of a series of tertiary and secondary carboranyl amines. Both amination reactions proceeded under mild conditions without the addition of any external oxidants. Hydrogenolysis of the resultant product 4-N(CH2Ph)2-o-carborane afforded the primary carboranyl amine, 4-amino-o-carborane, in quantitative yield.

Ir-Catalyzed –COOH directed site-selective B–H/C–H dehydrogenative cross-coupling of o-carborane with thiophenes has been achieved for the first time. Without any pre-functionalization, carboranyl carboxylic acids and thiophenes can serve as suitable coupling partners, resulting in the preparation of 4-thienyl-o-carboranes in a simple one-pot process for potential applications in materials.