Nucleophilic substitution: a facile strategy for selective B–H functionalization of carboranes

Abstract

Vertex-specific functionalization of carboranes has received considerable research interest, due to the valuable application of carborane derivatives in medicine, coordination/organometallic chemistry and materials. In comparison with a protic cage C-H bond, cage B-H is hydridic and generally less polar, with a bond dissociation energy of ca. 108 kcal mol^-1. These features make B-H activation quite different from that of the C-H bond. In addition, selectivity among ten very similar BH vertices in o-carborane is challenging yet crucial to the effective construction of carborane-based functional molecules. To address these issues, a brand new strategy of cage B-H nucleophilic substitution has recently been presented and developed for straightforward and regioselective cage B-H functionalization. The regioselectivity can be controlled by the electronic/steric properties of the cage carbon substituents. This Frontier article highlights the recent advancement in the nucleophilic cage B-H substitution of carboranes.