Palladium Catalyzed Selective B(3)-H Activation/Oxidative Dehydrogenative Coupling for the Synthesis of Bis(o-carborane)s.

A palladium catalyzed selective B(3)-H activation/oxidative dehydrogenative coupling for the synthesis of bis(o-carborane)s connected with B(3)-B(3') and B(3)-B(6') bonds has been developed for the first time. A plausible mechanism involving stepwise activation of B(3)-H and B(3'/6')-H bonds by PdII and PdIV was proposed. This work is the first example and the most efficient protocol for synthesis of bis(o-carborane)s connected with B(3)-B(3') and B(3)-B(6') bonds, which has important reference for design, synthesis, and application of bis(o-carborane)s in related fields.