Hydrogen peroxide oxidation of saturated hydrocarbons catalyzed by osmium compounds

Osmium derivatives, in particular OsCl3, catalyze the effective oxidation of saturated hydrocarbons in acetonitrile. The products formed are a ketone (aldehyde) and an alcohol. The addition of nitrogen heterocycles, such as pyridine, accelerated the reaction and increased the product yields. The ketone (aldehyde)/alcohol ratio dramatically changed in this case. In the presence of pyridine, the reaction occurred stereoselectively. The suggested reaction mechanism includes hydrogen atom abstraction from an alkane by an osmium oxo compound, resulting in the formation of the alkyl radical, which yields the alkylperoxyl radical after addition of an oxygen molecule. The latter radical degrades in the presence of the osmium complex under reaction conditions to give a ketone (aldehyde) and an alcohol.