Cu(OTf)/NBS-Mediated Tandem Reaction of 1-Cinnamyl Alcohol--Carboranes via Ring Opening of Oxetane with Arenes: An Alternative Approach for the Synthesis of C-Alkenyl--Carboranes.

The Cu(OTf)/NBS-mediated tandem reaction of 1-cinnamyl alcohol--carboranes for the synthesis of C-alkenyl--carboranes has been developed. Mechanism studies demonstrated that the Cu(OTf)-promoted ring opening of oxetane with electron-rich arenes as soft nucleophiles was involved and was the key step for the transformation. This work provided an alternative strategy for the synthesis of C-alkenyl--carboranes, which has an important reference for the synthesis of -carborane derivatives with diversity.

Old Key Opens the Lock in Carborane: The in Situ NHC-Palladium Catalytic System for Selective Arylation of B(3,6)-H Bonds of -Carboranes via B-H Activation.

An efficient in situ Pd-NHC catalytic system for regioselective arylation of B(3,6)-H bonds of -carborane has been developed for the first time. A series of symmetric and unsymmetric 3,6-diaryl--carboranes anchored with active groups have been synthesized with moderate to good yields under mild conditions. This work offers an efficient protocol for selective activation of B(3,6)-H bonds and has important value in design coupling reactions for selective functionalization of -carboranes.

Catalytic Oxidative Dehydrogenative Coupling of Cage B-H/B-H Bonds for Synthesis of Bis(-carborane)s.

An efficient and succinct protocol for synthesis of bis(-carborane) connected by a B-B bond via palladium catalyzed oxidative dehydrogenative coupling of cage B-H/B-H bonds was developed for the first time. A series of bis(-carborane)s connected by B(4)-B(4)' and B(4)-B(5)' bonds was synthesized with moderate to good yields. This work opens the door for miscellaneous applications of bis(-carborane) in related disciplines and has important value in design and synthesis of different kinds of biscarboranes.