Aerobic Oxidation of Alcohols Catalysed by Cu(I)/NMI/TEMPO System and Its Mechanistic Insights
Abstract Homogeneous Cu(I)/NMI/TEMPO catalyst system (TEMPO = 2,2,6,6-tetramethylpiperidine-N-oxyl) has been investigated for its catalysis on the aerobic oxidation of 1-octanol and other alcohols into aldehydes under room temperature. The catalytic species was found to be a Cu(I) centre coordinated by two NMI molecules and other two weakly bound solvent molecules, [Cu(NMI) 2 (Sol) 2 ] + (Sol = solvent). When CuI was used, this species could be [Cu(NMI)I(Sol) 2 ]. Not like being speculated previously, NMI in this system acts solely as a ligand and its role coordinated to the copper centre enhanced the electron density on the metal centre which promoted the O 2 binding in the catalysis. The labile solvent binding to the Cu(I) centre is essential to ensure both oxygen and substrate binding. The catalyst system is suitable for the oxidation of various alcohols using a simple reaction setup and workup. In particular, the system possesses strong oxidizing capability in quantitative conversion of benzylic alcohols regardless of the substituents on the phenyl ring and allylic alcohols into aldehydes. A plausible mechanism was also proposed for the catalysis. Graphical Abstract The aerobic oxidation of primary alcohols at room temperature to corresponding aldehydes was achieved by the catalyst composed by Cu(I) and methyl imidazole (NMI) mediated by TEMPO in acetonitrile. The catalytic species is proposed to be such a Cu(I) complex that two of its four coordinating sites are occupied by a strong ligand(s) and the rest two are weakly bound by solvent molecules.
危险品化学品经营许可证（带存储）