In conclusion, we have shown that N-heterocyclic carbene (NHC) borane B1 behaves as an efficient XAT agent for the activation of organic iodides. The formed nucleophilic radical can subsequently be engaged in a conjugate addition to generate the targeted C(sp 3 )-C(sp 3 ) bond. Notably, the transformation can be performed under UV-light by exploiting a radical chain mechanism, as well as extended to the visible range by adopting milder photoredox conditions.