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Updated: Jan 15, 2026

Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions
Published on: July 30, 2017
Carbamoylation of Aryl and Benzyl Chlorides by Direct C-H Functionalization of Formamide Derivatives via
Jihye Shin1, Eunseo Sim1, Sun Dongbang1,2
1Department of Chemistry, Sogang University, Mapo-gu, Seoul 04107, Republic of Korea.
Abstract:
We report a Ni/photoredox dual catalytic protocol that activates the formyl C-H bond of simple formamides to enable C(sp2)-C(sp2)/C(sp2)-C(sp3) 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(sp3)-H functionalization chemistry.
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