Photoredox B–H functionalization to selective B–N(sp³) coupling of nido-carborane with primary and secondary amines

Access to nido-carborane site-selective B–N(sp³) coupling by photoredox catalysed B–H activation has been achieved for the first time, which leads to the synthesis of a series of nitrogen-containing nido-carboranes with moderate to good yields. This protocol is applicable to primary and secondary amines containing alkyl, or heteroaryl groups as well as sulfonamides. Furthermore, the open to air and metal-free conditions with excellent site-selectivity represent a significant improvement for B–H functionalization of nido-carboranes with organic functionalities.