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Updated: Sep 15, 2025

Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions
Published on: July 30, 2017
Construction of Eight-Membered N-Heterocycles via Palladium-Catalyzed Cyclization of Allenyl Isocyanides
Haixia Zhao1, Yuchen Jiang1, Jingxuan Zhang1
1Key Laboratory of Functional Molecular Solids, Ministry of Education, Anhui Laboratory of Molecule-Based Materials (State Key Laboratory Cultivation Base), College of Chemistry and Materials Science, Anhui Normal University, Wuhu 241002, P.R. China.
Abstract:
A three-component construction of eight-membered nitrogen-containing heterocycles via palladium-catalyzed imidoylative cyclization of 2-isocyano-N-(propa-1,2-dien-1-yl)benzamides with aryl halides and carbon nucleophiles has been developed. Sequential isocyanide and allene insertion reactions facilitated the formation of medium-sized rings, overcoming the unfavorable transannular interactions and entropic factors, followed by an allylic substitution to yield benzodiazocine derivatives under mild reaction conditions. When the nucleophile was linked with aryl iodide, challenging diazocine-fused macrocycles could be accessed through an intramolecular allylic substitution process.
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