Saito I, Nagata R, Nakagawa H, Moriyama H, Matsuura T, Inoue K
Department of Synthetic Chemistry, Faculty of Engineering, Kyoto University, Japan.
Free Radic Res Commun. 1987;2(4-6):327-36. doi: 10.3109/10715768709065299.
Application of newly-developed water-soluble singlet oxygen sources in the oxidation of biologically important compounds and the electron-transfer process involving singlet oxygen has been reviewed. Particularly, oxidation products of tryptophan by chemically generated singlet oxygen were compared to those obtained in dye-sensitized photooxygenation. The usefulness of trimethylsilyl cyanide as a trapping reagent for dipolar peroxide intermediates has been demonstrated in the photooxygenation of N-methylindoles, 2-(methoxymethylene)adamantane and adamantylideneadamantane in aprotic solvents. Based on these trapping reactions mechanism of singlet oxygen reaction of electron-rich enol ethers and enamines is discussed in light of theoretical calculation.
本文综述了新开发的水溶性单线态氧源在生物重要化合物氧化以及涉及单线态氧的电子转移过程中的应用。特别地,将化学产生的单线态氧氧化色氨酸的产物与染料敏化光氧化得到的产物进行了比较。在非质子溶剂中,三甲基硅基氰化物作为捕获偶极过氧化物中间体的捕获试剂,已在N-甲基吲哚、2-(甲氧基亚甲基)金刚烷和亚金刚烷基金刚烷的光氧化中得到证实。基于这些捕获反应,根据理论计算讨论了富电子烯醇醚和烯胺的单线态氧反应机理。