Alkanes (n-heptane, 2- and 3-methylhexane, cis- and tuans-decalin) are readily oxidized under air in acetonitrile by the O-2-H2O,-PCA-VO3 reagent at room temperature to produce alkyl hydroperoxides as main products as well as minor amounts of the corresponding alcohols and carbonyl compounds. The site selectivities of the reactions are very similar to those observed with hydroxylation of the alkanes with hydrogen peroxide under UV irradiation. The proposed mechanism involves the catalytic formation of hydroxyl radicals from hydrogen peroxide which abstract hydrogen atoms from the alkanes. The alkyl radicals react rapidly with molecular oxygen to produce peroxyl radicals which are transformed mainly into the hydroperoxides. Copyright (C) 1996 Elsevier Science Ltd.52411305113062