基于四氮配体的铜配合物/TEMPO催化的苄醇与烯丙基醇的氧化反应

摘要

发展了非血红素类四氮配体的铜配合物和2,2,6,6-四甲基哌啶-氮-氧自由基(TEMPO)相结合的催化体系,应用于分子氧参与的伯醇氧化反应。该体系具有条件温和、高效、高选择性、无需任何助剂和底物(包括苄醇、烯丙基醇和含杂原子伯醇)使用性强等优点。此外,利用高分辨质谱和紫外-光谱等对反应活性中间体进行了初步探讨。%A new system consisting of a copper(I) complex generated in situ from a tetradentate nitrogen lig-and and CuI in combination with 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) derivatives was successfully developed. The system was suitable for efficient and selective aerobic oxidation of primary benzyl and allyl alcohols with a wide range of functional groups to the corresponding al-dehydes at room temperature. The best result was obtained with N,N'-dimethyl-N,N'-bis(2-pyri-dylmethyl)ethane-1,2-diamine as the ligand and 4-OH-TEMPO as a cocatalyst in CH3CN. In addition, high-resolution mass spectrometry, ultraviolet-visible spectroscopy, and electrochemical experi-ments were used to provide evidence of intermediates.