Construction of Safer Oxidation Systems

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1. New Protocol for Oxidation in Water : Micellar Oxidation Systems Composed of α-AHPA series of novel amphiphilic hydroperoxides, α-alkoxyalkyl hydroperoxides (α-AHP) and their related hydroperoxides, were prepared with the intention of developing new oxidizing agents bearing a micelle-forming character in water. Both oxidation of benzyl sulfide and epoxidation of geraniol promoted by these hydroperoxides were investigated in detail under various conditions. Because the conversion of each substrate in the micellar systems was higher than that in nonmicellar media, the solubilization of substrates into micelles was certainly effective in promoting oxidations of insoluble substrates in aqueous media.2. Safer Oxidation Systems Composed of Oxone and Amphiphilic Ketones in WaterNew nonionic surfactant bearing a carbonyl group at the terminal position of hydrophilic moiety were prepared and were applied to newly designed micellar aqueous oxidation systems composed of Oxone (2KHSO_5-KHSO_4・K_2S0_4) as an oxidizing agent. Both solubilization of substrates by micelles of these surfactants and active peroxo species generated by the reaction of these surfactants with Oxone in situ were the keys in promoting effective epoxidation of various alkenes in water.3. Radical Cyclization Initiated by the Reaction of Allylic Hydroperoxides with FeSO_4 in Aqueous MediaTreatment of 1-methyl-2-methylene-1-cyclohexane with a mixture of FeSO_4/CuCl_2 in aqueous media yielded 1-(1-chlorocyclohexyl)ethanones as the major product consistent with 6-endo-trig cyclization of the intermediate alkyl radical. This strategy was extended to the ring enlargement of a series of 1 -isopropylcycloalkyl hydroperoxides. Regioselective 7-or 8-endo-trig cyclization reactions could be achieved by treatment of the corresponding cyclopentyl or cyclohexyl hydroperoxides with a mixture of FeSO_4/CuCl_2 in aqueous media.