Facile Synthesis of Nitrogen Tetradentate Ligands and Their Applications in CuI‐Catalyzed N‐Arylation and Azide–Alkyne Cycloaddition

Five new tetradentate ligands NNNN] with benzimidazolyl‐imine or amine nitrogen donors have been synthesized in good yields under mild conditions from easily available substrates. trans‐N,N′‐bis(1‐Ethyl‐2‐benzimidazolylmethylene)cyclohexane‐1,2‐diimine is the best accelerating ligand in this series that supports the Cu^I‐catalyzed Ullmann N‐arylation and the direct three‐component azide–alkyne cycloaddition reaction to give the corresponding substituted imidazole, pyrazole, and triazole in high yields. Single‐crystal X‐ray diffraction analysis of its complex with CuI reveals a novel one‐dimensional coordination polymer of the metal chain bridged alternately by the NNNN] ligand and diiodides.