Reduction of alkyl hydroperoxides to alcohols: Role of rubredoxin, an electron carrier in the bacterial hydroxylation of hydrocarbons

Abstract

Alkyl hydroperoxides are reduced to alcohols in the presence of DPNH and homogeneous rubredoxin and rubredoxin-DPN reductase from Pseudomonas oleovorans . The reaction does not occur when TPNH is substituted for DPNH or when rubredoxins from anaerobic bacteria are substituted for the P. oleovorans nonheme iron protein. The reaction appears to have broad substrate specificity; 1-octyl, 2-octyl, cyclohexyl, and cymyl hydroperoxides are all reduced at significant rates. The reduction of alkyl hydroperoxides is inhibited by cyanide, as is the hydroxylation of alkanes and fatty acids in the same enzyme system supplemented with the ω-hydroxylase.