Cu‐UiO‐66 Catalyzed Oxidative Coupling of Primary Amines for Imine Synthesis

ABSTRACT Herein, a highly active Cu‐UiO‐66 catalyst was constructed by precisely anchoring monodisperse Cu sites through Zr 6 ‐oxo cluster nodes, which enabled efficient oxidative coupling of primary amines under mild conditions with 98% imine yield. The catalytic system used oxygen in air as the oxidant, and no noble metal or strong chemical oxidant was required. The high selectivity of imine was achieved by inhibiting further oxidation of the C═N bond through the pore‐limited domains of metal‐organic frameworks (MOFs) and Cu site synergy. As a result of experimental and characterization results, Cu doping was found to significantly increase the oxygen vacancy concentration, enhance the electron transfer efficiency, and promote the generation of the key active species O 2 ·− . In addition, Cu‐UiO‐66 exhibits excellent cycling stability (≥ 5 cycles) and maintains superior catalytic activity. Cu‐UiO‐66 solves the problems of low selectivity and harsh conditions in imine synthesis through its unique structural properties.