Palladium-Catalyzed Regioselective Diarylation of o-Carboranes By Direct Cage B-H Activation.

Palladium-catalyzed intermolecular coupling of o-carborane with aromatics by direct cage B-H bond activation has been achieved, leading to the synthesis of a series of cage B(4,5)-diarylated-o-carboranes in high yields with excellent regioselectivity. Traceless directing group -COOH plays a crucial role for site- and di-selectivity of such intermolecular coupling reaction. A Pd(II)-Pd(IV)-Pd(II) catalytic cycle is proposed to be responsible for the stepwise arylation.