An atom-economical method for the direct B À H functionalization of nido-carboranes (7,8-nido-C 2 B 9 H 12 À)h as been developed under electrochemical reaction conditions.I n this reaction system, anodic oxidation serves as ag reen alternative for traditional chemical oxidants in the oxidation of nido-carboranes.N ot ransition-metal catalyst is required and different heteroatoms bearing al one pair are reactive in this transformation. Coupling nido-carboranes with thioethers, selenides,t ellurides,N-heterocycles,p hosphates,p hosphines, arsenides and antimonides demonstrates high site-selectivity and efficiency.I mportantly,n ido-carboranes can be easily incorporated into drug motifs through this reaction protocol.

Functionalization of carboranes in a vertex‐specific manner is a perennial challenge. Here, we report a photocatalytic B−C coupling for the selective functionalization of carboranes at the boron site which is most distal to carbon. This reaction was achieved by the photo‐induced decarboxylation of carborane carboxylic acids to generate boron vertex‐centered carboranyl radicals. Theoretical calculations also demonstrate that the reaction more easily occurs at the boron site bearing higher electron density owing to the lower energy barrier for a single‐electron transfer to generate a carboranyl radical. By using this strategy, a number of functionalized carboranes could be accessed through alkylation, alkenylation, and heteroarylation under mild conditions. Moreover, both a highly efficient blue emitter with a solid‐state luminous efficiency of 42 % and a drug candidate for boron neutron capture therapy (BNCT) containing targeting and fluorine units were obtained.

An atom‐economical method for the direct B−H functionalization of nido‐carboranes (7,8‐nido‐C2B9H12−) has been developed under electrochemical reaction conditions. In this reaction system, anodic oxidation serves as a green alternative for traditional chemical oxidants in the oxidation of nido‐carboranes. No transition‐metal catalyst is required and different heteroatoms bearing a lone pair are reactive in this transformation. Coupling nido‐carboranes with thioethers, selenides, tellurides, N‐heterocycles, phosphates, phosphines, arsenides and antimonides demonstrates high site‐selectivity and efficiency. Importantly, nido‐carboranes can be easily incorporated into drug motifs through this reaction protocol.

The site-selective functionalization … … of carboranes with multiple B À H sites is a long-standing challenge. In their Research Article (e202205672), Deshuang Tu, Changsheng Lu, Hong co-workers developed an efficient reaction protocol for the selective alkylation, alkenylation, and heteroarylation of carboranes under mild conditions via boron-vertex-centered carboranyl radicals generated by photo-induced decarboxylation of boron-substituted carborane carboxylic acids.

Functionalization of carboranes in a vertex‐specific manner is a perennial challenge. Here, we report a photocatalytic B−C coupling for the selective functionalization of carboranes at the boron site which is most distal to carbon. This reaction was achieved by the photo‐induced decarboxylation of carborane carboxylic acids to generate boron vertex‐centered carboranyl radicals. Theoretical calculations also demonstrate that the reaction more easily occurs at the boron site bearing higher electron density owing to the lower energy barrier for a single‐electron transfer to generate a carboranyl radical. By using this strategy, a number of functionalized carboranes could be accessed through alkylation, alkenylation, and heteroarylation under mild conditions. Moreover, both a highly efficient blue emitter with a solid‐state luminous efficiency of 42 % and a drug candidate for boron neutron capture therapy (BNCT) containing targeting and fluorine units were obtained.