Zaccheria Federica, Ravasio Nicoletta, Psaro Rinaldo, Fusi Achille
Dip. CIMA, Università degli Studi di Milano, Via G. Venezian 21, 20133 Milano, Italy.
Chemistry. 2006 Aug 16;12(24):6426-31. doi: 10.1002/chem.200501619.
A method for the anaerobic oxidation of a wide series of alcohols including cyclohexanols and steroidal alcohols, has been set up. It relies on a transfer dehydrogenation reaction from the substrate alcohol to styrene catalyzed by a heterogeneous, reusable copper catalyst under very mild liquid-phase experimental conditions (90 degrees C, N(2)) and shows unusual selectivity. Thus, the method is selective for the oxidation of secondary and allylic alcohols even in the presence of unprotected primary and benzylic alcohols. Electronic effects and the choice of the hydrogen acceptor account for the selectivity observed.
已建立一种用于多种醇（包括环己醇和甾体醇）厌氧氧化的方法。该方法依赖于在非常温和的液相实验条件（90℃，氮气）下，由非均相、可重复使用的铜催化剂催化底物醇与苯乙烯之间的转移脱氢反应，并且具有不同寻常的选择性。因此，即使存在未受保护的伯醇和苄醇，该方法对仲醇和烯丙醇的氧化仍具有选择性。观察到的选择性归因于电子效应和氢受体的选择。
