Iridium-Catalyzed Regioselective B(4)-Alkenylation and B(3,5)-Dialkenylation of o-Carboranes.

Iridium(I)-catalyzed regioselective B(4)-alkenylation has been developed from o-carboranyl sulfoxonium ylides and alkynes through B(4)-H activation. The sequential B(4)- and B(6)-alkenylation afforded B(3,5)-dialkenylated o-carboranyl sulfoxonium ylides in one pot. Eventually, two alkenyl groups, the same or different, were introduced at positions 3 and 5 of the carborane. Sulfoxonium ylide used as a directing group remains available for further functionalization and is converted to B-alkenylated o-carboranyl trichloromethyl ketones.