High-yield epoxidations with hydrogen peroxide and tert-butyl hydroperoxide catalyzed by iron(III) porphyrins: heterolytic cleavage of hydroperoxides

摘要: The reactions of hydrogen peroxide or tert-butyl hydroperoxide with cyclooctene and norbornene, catalyzed by iron(III) tetrakis(pentafluorophenyl)porphyrin chloride other electronegatively-substituted porphyrins, produced 60-100% epoxide yields. epoxynorbornane yield has the same ratio exo/endo isomers as is obtained using pentafluoroiodosylbenzene, an oxidant which produces iron(IV) radical cation (oxene) intermediate. These results demonstrate heterolytic cleavage these peroxides in reaction