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Nucleophilic substitution: a facile strategy for selective B-H functionalization of carboranes
Yangjian Quan1, Cen Tang, Zuowei Xie
1Department of Chemistry and State Key Laboratory of Synthetic Chemistry, The Chinese University of Hong Kong, Shatin, New Territories, Hong Kong, China. zxie@cuhk.edu.hk.
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.
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