Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 10, Issue 19, Pages 4728-4734Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.200400352
Keywords
alcohols; allylic compounds; epoxidation; reaction mechanisms; tungsten
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The highly chemo-, regio-, and diastereoselective and stereospecific epoxidation of various allylic alcohols with only one equivalent of hydrogen peroxide in water can be efficiently catalyzed by the dinuclear peroxotungstate, K-2[{W(=O)(O-2)(2)(H2O)}(2)(mu-O)].2H(2)O (I). The catalyst is easily recycled while maintaining its catalytic performance. The catalytic reaction mechanism including the exchange of the water ligand to form the tungsten-alco-holate species followed by the insertion of oxygen to the carbon-carbon double bond, and the regeneration of the dinuclear peroxotungstate with hydrogen peroxide is proposed. The reaction rate shows first-order dependence on the concentrations of allylic alcohol and di-nuclear peroxotungstate and zero-order dependence on the concentration of hydrogen peroxide. These results, the kinetic data, the comparison of the catalytic rates with those for the stoichiometric reactions, and kinetic isotope effects indicate that the oxygen transfer from a dinuclear peroxotungstate to the double bond is the rate-limiting step for terminal allylic alcohols such as 2-propen-1-ol (1a).
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