Palladium catalyzed selective mono-arylation of o-carboranes with aryl iodides has been developed, and a series of B(8)/B(9)-Ar-o-carboranes anchored with active groups have been synthesized with moderate to good yield as well as good selectivity. The mechanism involving Pd^II catalyzed electrophilic B–H activation was also proposed.

A palladium catalyzed/silver tuned selective mono- and tetra-acetoxylation of o-carboranes has been developed, and a series of mono- and tetra-acetoxylated o-carboranes decorated with active groups have been synthesized with moderate to good yields as well as excellent selectivity. A mechanism involving electrophilic palladation and cyclopalladation of the B–H bond was proposed.

A regioselective mono-alkenylation of o-carboranes on B(8) and B(9) via palladium catalyzed Heck type coupling of a cage B–H bond has been developed, and kinds of B(8)/B(9)-alkenyl-o-carboranes decorated with active groups have been synthesized with moderate yield as well as good regioselectivity. A Pd^II catalyzed electrophilic B–H activation mechanism was also proposed.

By changing the charge distribution of boron vertices via introducing an amide on cage B(9), the selective B(4) arylation of o-carboranes via Suzuki–Miyaura coupling has been developed. A series of o-carborane derivatives decorated with diverse active groups have been synthesized with moderate to good yields, which have been proved to be further transformed to a novel kind of tri-substituted nido-carborane fused oxazole with potential application in boron neutron capture therapy, organometallic as well as coordination chemistry.