Catalytic oxygenation of alkenes and alkanes by oxygen donors catalyzed by cobalt-substituted polyoxotungstate

Abstract

The cobalt-substituted polyoxotungstate [(CoPW11O39)5-] has been used as a catalyst in olefin epoxidation and alkane hydroxylation reactions. The epoxidation of olefins by iodosylbenzene in CH3CN yielded epoxides predominantly with trace amounts of allylic oxidation products. cis-Stilbene was streoselectively oxidized to cis-stilbene oxide with small amounts of trans-stilbene oxide and benzaldehyde formation. The epoxidation of carbamazepine (CBZ) by potassium monopersulfate in aqueous solution gave the corresponding CBZ 10,11-oxide product. Other transition metal-substituted polyoxotungstates (M = Mn2+, Fe2+, Ni2+, and Cu2+) were inactive in the CBZ epoxidation reaction. The cobalt-substituted polyoxotungstate also catalyzed the oxidation of alkanes with m-chloroperbenzoic acid to give the corresponding alcohols and ketones. The presence of CH2Br2 in the hydroxylation of cyclohexane afforded the formation of bromocyclohexane, suggesting the participation of cyclohexyl radical. In the 18O-labeled water experiment, there was no incorporation of 18O into the cyclohexanol product when the hydroxylation of cyclohexane by MCPBA was carried out in the presence of H218O. Some mechanistic aspects are discussed as well.