Carbamoylation of Aryl and Benzyl Chlorides by Direct C–H Functionalization of Formamide Derivatives via Ni/Photoredox-Catalyzed Cross-Coupling

We report a Ni/photoredox dual catalytic protocol that activates the formyl C–H bond of simple formamides to enable C(sp 2 )–C(sp 2 )/C(sp 2 )–C(sp 3 ) carbamoylation with aryl and benzyl chlorides. This transformation proceeds without the need for prefunctionalized carbamoyl radical precursors, external oxidants, or halogen atom transfer (XAT)/hydrogen atom transfer (HAT) reagents by harnessing in situ -generated Cl radicals for selective HAT followed by the cross-coupling event. This strategy provides a mild and atom-economical platform for accessing structurally diverse amides, including sterically hindered variants that are difficult to access through classical C–N bond-forming methodologies. Stoichiometric studies of independently synthesized Ni complexes reveal a distinct pathway involving a Ni(II)(carbamoyl)Cl complex as the active intermediate, diverging from the previously established C(sp 3 )–H functionalization chemistry.