Design of a GO/Fe₃O₄-Supported Cu(I) Nanocatalyst for Three-Component Sulfonamide Synthesis via SO₂ Insertion in DES Solvent
摘要
We report the rational design, synthesis, and comprehensive evaluation of a novel heterogeneous copper(I) nanocatalyst, designated GO/Fe₃O₄–Mel/Tet–CuI, that can be readily recovered by magnetic separation. The material arises from a stepwise functionalization of graphene oxide with Fe₃O₄ nanoparticles, melamine, and tetrazole ligands, followed by immobilization of CuI species, yielding a hybrid organic–inorganic nanocomposite with a high surface area, a nitrogen-rich coordination environment, and superparamagnetic behavior. Extensive characterization by FT-IR, XRD, SEM, TEM, EDX, ICP-OES, BET, TGA, and VSM confirmed successful construction, preserved structural integrity, thermal stability, and robust magnetic properties. The catalyst was then applied to the three-component synthesis of N-arylsulfonamides via sulfur dioxide insertion, using potassium metabisulfite as a safe and economical SO₂ surrogate. Under optimized conditions, a broad array of aryl iodides and amines were converted to the corresponding sulfonamides in high yields (83–98%), with strong tolerance to diverse functional groups, underscoring the method’s versatility in synthetic chemistry. Notably, the catalyst demonstrated outstanding stability and recyclability, maintaining high activity over eight consecutive cycles with negligible copper leaching. Mechanistic investigations support a Cu(I)/Cu(III) catalytic cycle stabilized by the nitrogen-rich ligand framework integrated into the GO–Fe₃O₄–Mel/Tet scaffold.
Graphical Abstract