Ir-catalyzed selective dehydrogenative cross-coupling of aryls with o-carboranes via a mixed directing-group strategy.

An efficient Ir-catalyzed selective B-H/C-H dehydrocoupling between o-carboranes and (hetero)aryls has been achieved based on a mixed directing-group strategy, leading to a wide variety of carborane-(hetero)arene combinations. Control experiments indicate that aryl C-H activation proceeds preferentially over the B-H one. Thus, a plausible reaction pathway for dehydrogenative cross-coupling is proposed after the characterization of a key intermediate.