Ferroxime(II)-catalyzed oxygenation of nitroalkanes by tert-butyl hydroperoxide and its relevance to 2-nitropropane dioxygenase

Abstract

The complex [Fe(Hdmg) 2(py) 2], referred to as ferroxime(II), was found to be a selective catalyst for the oxidative denitrification of nitroalkanes such as 1-nitroethane, 1-nitropropane, 2-nitropropane, 1-nitropentane and nitrocyclohexane to the corresponding aldehydes or ketones. The oxidation was performed in DMF and EtOH under Ar in the presence of various oxidants such as O 2, TBHP, H 2O 2 at room temperature, and was followed by glc. The substrate specificity of the catalyst either in DMF or EtOH solution shows that there are no significant differences in the conversions with the exception of 1-nitropentane and nitrocyclohexane. The effect of various oxidants shows that the catalytic oxidations were effective only with TBHP and H 2O 2. No oxidation products could be detected when O 2 was used. The best conversions (TN) have been obtained with TBHP in EtOH (up to 24%, TN=9.3), followed by H 2O 2 (1.7%, TN=0.5).