Polymeric Complex of 1-Phenylsulfanyl/selenylmethyl-1H-Benzotriazole with Ag(I): Pre-catalystfor A³Coupling Affording Propargylamines on aGram/Lab Scale

A3 coupling of aldehyde, amine and phenylacetylene catalyzed with [AgL1/L2(amine)]+ generated in situ from a polymeric complex[{Ag(μ-L1/L2)NO3}n] where L1=1-phenylsulfanylmethyl-1H-benzotriazole and L2=1-phenylselenylmethyl-1H-benzotriazole) was found suitable for gram and lab scale synthesis of propargylamines (Yield up to 88 and 94 %, respectively) at 60 °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 °C resulted in [{Ag(μ-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 1H, 13C{1H} and 77Se{1H} 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) A, respectively.