Nickel-catalyzed switchable and regioselective iterative B–H arylation of carborane clusters

Abstract

The B–H activation selectivity of carborane clusters constitutes a formidable challenge in boron cluster chemistry, particularly for the development of sustainable synthetic protocols that bypass precious metals and overcome inherent selectivity limitations. Here, we show that such a challenge could be addressed using nickel catalysis, thereby enabling a broadly useful strategy for carborane polyarylation with complementary site-selectivity. Mechanistic investigations reveal two distinct substrate-controlled activation modes: a “cage-walking” process and an orthogonal steric hindrance-directed pathway. These complementary pathways enable precise molecular editing of carborane scaffolds, furnishing a diverse library of functionalized derivatives. This modular platform further streamlines the synthesis of poly-functionalized carboranes, expanding the synthetic toolkit of carborane chemistry and laying a robust foundation for advanced boron-based materials and therapeutics.