Nardello Véronique, Caron Laurent, Aubry Jean-Marie, Bouttemy Sabine, Wirth Thomas, Saha-Möller Chantu R, Adam Waldemar
LCOM, Equipe de Recherches "Oxydation et Formulation", UMR CNRS 8009, ENSCL BP 108, F-59652 Villeneuve d'Ascq Cedex, France.
J Am Chem Soc. 2004 Sep 1;126(34):10692-700. doi: 10.1021/ja048589f.
The chiral allylic alcohols 1a-d and their acetate (1e) and silyl ether (1f) derivatives have been oxidized by the H2O2/MoO4(2)- system, a convenient and efficient chemical source of singlet oxygen. This chemical peroxidation (formation of the allylic hydroperoxides 2) has been conducted in various media, which include aqueous solutions, organic solvents, and microemulsions. The reactivity, chemoselectivity, and diastereoselectivity of this chemical oxidation are compared to those of the sensitized photooxygenation, with the emphasis on preparative applications in microemulsion media. While a similar threo diastereoselectivity is observed for both modes of peroxidation, the chemoselectivity differs significantly, since in the chemical oxidation with the H2O2/MoO4(2)- system the undesirable epoxidation by the intermediary peroxomolybdate competes efficiently with the desirable peroxidation by the in situ generated singlet oxygen. A proper choice of the type of microemulsion and the reaction conditions furnishes a high chemoselectivity (up to 97%) in favor of threo-diastereoselective (up to 92%) peroxidation.
手性烯丙醇1a - d及其乙酸酯（1e）和硅醚（1f）衍生物已通过H2O2/MoO4(2)-体系进行氧化，该体系是一种方便且高效的单线态氧化学源。这种化学过氧化反应（生成烯丙基氢过氧化物2）已在包括水溶液、有机溶剂和微乳液在内的各种介质中进行。将这种化学氧化的反应性、化学选择性和非对映选择性与敏化光氧化反应的相关性质进行了比较，重点是在微乳液介质中的制备应用。虽然两种过氧化模式都观察到了相似的苏式非对映选择性，但化学选择性有显著差异，因为在H2O2/MoO4(2)-体系的化学氧化中，中间过氧钼酸盐引起的不希望发生的环氧化反应与原位生成的单线态氧引发的理想过氧化反应有效竞争。对微乳液类型和反应条件的适当选择可提供高达97%的高化学选择性，有利于苏式非对映选择性高达92%的过氧化反应。
