A general method for the oxidative substitution of nido‐carborane (7,8‐C2B9H12−) with N‐heterocycles has been developed by using 2,3‐dichloro‐5,6‐dicyanobenzoquinone (DDQ) as an oxidant. This metal‐free B−N coupling strategy, in both inter‐ and intramolecular fashions, gave rise to a wide array of charge‐compensated, boron‐substituted nido‐carboranes in high yields (up to 97 %) with excellent functional‐group tolerance under mild reaction conditions. The reaction mechanism was investigated by density‐functional theory (DFT) calculations. A successive single‐electron transfer (SET), B−H hydrogen‐atom transfer (HAT), and nucleophilic attack pathway is proposed. This method provides a new approach to nitrogen‐containing carboranes with potential applications in medicine and materials.

Ag eneral method for the oxidative substitution of nido-carborane (7,8-C 2 B 9 H 12 À )w ith N-heterocycles has been developed by using 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ) as an oxidant. This metal-free B À Ncoupling strategy, in both inter-a nd intramolecular fashions,g ave rise to aw ide arrayo fc harge-compensated, boron-substituted nido-carboranes in high yields (up to 97 %) with excellent functional-group tolerance under mild reaction conditions.T he reaction mechanism was investigated by density-functional theory (DFT) calculations.Asuccessive single-electron transfer (SET), BÀH hydrogen-atom transfer (HAT), and nucleophilic attackp athway is proposed. This method provides an ew approach to nitrogen-containing carboranes with potential applications in medicine and materials.

Access to nido-carborane site-selective B–N(sp3) coupling by photoredox catalyzed B–H activation has been achieved for the first time, which leads to the synthesis of a series of nitrogen-containing nido-carboranes in...

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