Rhodium(III)-Catalyzed Alkenylation-Annulation of closo-Dodecaborate Anions through Double B-H Activation at Room Temperature

1,2,3-Trisubstituted closo-dodecaborates with B-O, B-N, and B-C bonds as well as a fused borane oxazole ring have been synthesized by rhodium-catalyzed direct cage B-H alkenylation and annulation of ureido boranes in the first reported example of regioselective B-H bond functionalization of the [B12H12](2-) cage by transition-metal catalysis. This reaction proceeded at room temperature under ambient conditions and exhibited excellent selectivity for efficient monoalkenylation with good functional-group tolerance. The urea moiety enabled B-H activation by acting as a directing group, was incorporated in the oxazole ring in situ, and also avoided multiple alkenylation. A possible mechanism is proposed on the basis of the isolation of a rhodium agostic intermediate and control experiments.