New Protocol for Oxidation in Water:  Micellar Oxidation Systems Composed of Novel Amphiphilic Hydroperoxides

A series of novel amphiphilic hydroperoxides, α-alkoxyalkyl hydroperoxides (α-AHPs) and their related hydroperoxides, were designed and prepared with the intention of developing new oxidizing agents bearing a micelle-forming character in water. After their fundamental physical and interfacial properties were elucidated, both oxidation of benzyl sulfide and epoxidation of geraniol promoted by these hydroperoxides were investigated in detail under various conditions. Effective oxidation of benzyl sulfide to the corresponding sulfoxide was achieved in aqueous micellar systems composed of α-AHPs 1a−d and a catalytic amount of MoO₂(acac)₂ at 30 °C. Up to 100% conversion was observed under the optimum conditions. In the case of epoxidation of geraniol in water, the corresponding 2,3-epoxide was selectively formed in good yields. 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. Micellar oxidation systems composed of novel amphiphilic hydroperoxides afford a new protocol in order to derive safer conditions under which these reactions may be carried out.