催化学报
催化學報
최화학보
CHINESE JOURNAL OF CATALYSIS
2014年
11期
1864-1873
,共10页
张淑芳%苗成霞%徐大乾%孙伟%夏春谷
張淑芳%苗成霞%徐大乾%孫偉%夏春穀
장숙방%묘성하%서대건%손위%하춘곡
醇%需氧氧化%四氮配体%铜%2,2,6,6-四甲基哌啶-氮-氧自由基
醇%需氧氧化%四氮配體%銅%2,2,6,6-四甲基哌啶-氮-氧自由基
순%수양양화%사담배체%동%2,2,6,6-사갑기고정-담-양자유기
Alcohol%Aerobic oxidation%Tetradentate nitrogen ligand%Copper%2,2,6,6-tetramethylpiperidine-1-oxyl
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。
髮展瞭非血紅素類四氮配體的銅配閤物和2,2,6,6-四甲基哌啶-氮-氧自由基(TEMPO)相結閤的催化體繫,應用于分子氧參與的伯醇氧化反應。該體繫具有條件溫和、高效、高選擇性、無需任何助劑和底物(包括芐醇、烯丙基醇和含雜原子伯醇)使用性彊等優點。此外,利用高分辨質譜和紫外-光譜等對反應活性中間體進行瞭初步探討。
발전료비혈홍소류사담배체적동배합물화2,2,6,6-사갑기고정-담-양자유기(TEMPO)상결합적최화체계,응용우분자양삼여적백순양화반응。해체계구유조건온화、고효、고선택성、무수임하조제화저물(포괄변순、희병기순화함잡원자백순)사용성강등우점。차외,이용고분변질보화자외-광보등대반응활성중간체진행료초보탐토。
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.