HETEROGENEOUS PERMANGANATE OXIDATIONS: 3. MECHANISM OF THE OXIDATION OF ALCOHOLS BY HYDRATED COPPER PERMANGANATE.

Article abstract of DOI:10.1021/ja00348a038

Secondary alcohols dissolved in methylene chloride are readily oxidized to the corresponding ketones when treated with hydrated permanganate salts under heteorgeneous conditions. However, the addition of equimolar amounts of an alkene almost completely inhibits the reaction, apparently by formation of pi complexes on the surface of the oxidant. When mixtures of saturated secondary and beta , gamma -unsaturated alcohols are treated with hydrated copper permanganate, the unsaturated alcohols are preferentially oxidized, although the converse is true when each alcohol is oxidized separately. These observations suggest that unsaturated compounds must form organometallic complexes on the reactive sites of the reagent and that oxidation of unsaturated alcohols may be initiated by complexation of double bond followed by rearrangement within the coordination shell of manganese to give an oxygen complex that can be converted to the corresponding unsaturated ketone.