Amphiphilic Self-Assembled Polymeric Copper Catalyst to Parts per Million Levels: Click Chemistry

Abstract

Self-assembly of copper sulfate and a poly­(imidazole–acrylamide) amphiphile provided a highly active, reusable, globular, solid-phase catalyst for click chemistry. The self-assembled polymeric Cu catalyst was readily prepared from poly­(<i>N</i>-isopropylacrylamide-<i>co</i>-<i>N</i>-vinylimidazole) and CuSO₄ via coordinative convolution. The surface of the catalyst was covered with globular particles tens of nanometers in diameter, and those sheetlike composites were layered to build an aggregated structure. Moreover, the imidazole units in the polymeric ligand coordinate to CuSO₄ to give a self-assembled, layered, polymeric copper complex. The insoluble amphiphilic polymeric imidazole Cu catalyst with even 4.5–45 mol ppm drove the Huisgen 1,3-dipolar cycloaddition of a variety of alkynes and organic azides, including the three-component cyclization of a variety of alkynes, organic halides, and sodium azide. The catalytic turnover number and frequency were up to 209000 and 6740 h^–1, respectively. The catalyst was readily reused without loss of catalytic activity to give the corresponding triazoles quantitatively