Merging N‐Heterocyclic Carbene Organocatalysis with Hydrogen Atom Transfer Strategy

Abstract Radical N ‐heterocyclic carbene (NHC) organocatalysis has progressed significantly in recent years, enabling various incredible transformations. However, prefunctionalized substrates bearing a redox functionality were always required. As a result, the direct functionalization of aliphatic C−H bonds in simple substrates remains a challenge. This situation was changed once the hydrogen transfer atom (HAT) strategy was successfully applied in radical NHC catalysis very recently. This concept paper focused on the discussion of merging NHC catalysis with a classical intramolecular 1,5‐HAT process. Moreover, the unprecedented application of intermolecular HAT in radical NHC catalysis is highlighted as a novel catalysis model showing great synthetic promise.