Exploring amine-rich supramolecular silver(i) metallogels for autonomous self-healing and as catalysts for a three component coupling reaction

Abstract

A series of Ag(I) supramolecular organo-aqueous gels have been synthesized in the presence of an amine-rich triazole ligand as a gelator. Judicious choice of the triazole derivative and counter anion allows a desired spatial orientation of the pendant amine functionality to accentuate the gelation ability and autonomous self-healability via hydrogen bonding. In addition, the hydrogen bond donors, i.e. pendant –NH₂ groups, offer a critical proximity of counter anions to the Lewis acidic Ag(I) and the reactants for promoting a three component coupling reaction of an aldehyde, a terminal alkyne and an amine, giving expedient access to propargyl amines, with remarkable functional group tolerance for both aromatic and aliphatic aldehydes, and aryl acetylenes. Experiments substantiate the pivotal role of counter anions and H-bonding interactions in the observed preference for propargylamines over the diacetylene by-product. Our catalyst is robust, bench-stable, and recyclable, and demonstrates a catalytic efficiency comparable to or better than those of reported systems. The catalyst was found equally effective for the gram-scale synthesis of propargylamines. Our approach lies at the intersection of metal-based, H-bond-mediated counter anion-tuned catalysis, evincing a potential for the development of purpose-built supramolecular gels for desired catalytic applications in the future.