Polymeric Complex of 1-Phenylsulfanyl/selenylmethyl-1H-Benzotriazole with Ag (I): Pre-catalystfor A3 Coupling Affording Propargylamines on aGram/Lab Scale

A(3) coupling of aldehyde, amine and phenylacetylene catalyzed with [AgL1/L2(amine)](+) generated in situ from a polymeric complex[{Ag(mu-L1/L2)NO3} n] where L1= 1-phenyl-sulfanylmethyl-1H-benzotriazole and L2= 1-phenyl-selenylmethyl-1H-benzotriazole) was found suitable for gram and lab scale synthesis of propargylamines (Yield up to 88 and 94%, respectively) at 60 degrees C in 3 h. The catalytic process is simple and applicable to various combinations of aldehyde and amine substrates. 1-Chloromethyl-1H-benzotriazole was reacted with PhSNa and PhSeNa, generated in situ, to prepare ligands L1 and L2, respectively. The reactions of AgNO3 with L1 and L2in acetonitrile at 70 degrees C resulted in [{Ag(mu-L) NO3}(n)] (1 and 2, when L= L1 and L2respectively), stable under ambient conditions including light. The ligands and complexes have been characterized with H-1, C-13{H-1} and Se-77{H-1} NMR spectroscopy and mass spectrometry. The single crystal structures of 1 and 2 have been determined by X-ray diffraction. The Ag-S and Ag-Se bond lengths in 1 and 2are 2.466(2) and 2.5334(17) angstrom, respectively.