EPOXIDATION OF CIS-1,2-DIDEUTERIO-1-OCTENE BY PSEUDOMONAS-OLEOVORANS MONOOXYGENASE PROCEEDS WITHOUT DEUTERIUM-EXCHANGE

The mechanism of Pseudomonas oleovorans monooxygenase octene epoxidation was examined for possible iron carbene species along the epoxidation pathway. A deuterated olefin substrate (cis-1,2-dideuterio-1 -octene) was synthesized and the enzymatic product examined for deuterium content. No loss of the deuterium from carbon-2 of the olefin was observed during epoxidation of cis-1,2-dideuterio-1 -octene by P. oleovorans monooxygenase. This indicates that the epoxidation pathway of P. oleovorans monooxygenase does not involve the labilization of the hydrogen on carbon-2 of the olefin. We have previously reported that no exchange of deuterium from carbon-1 occurs during P. oleovorans monooxygenase epoxidation of either error trans-1 -deuterio-1 -octene. Thus, we see no evidence for the involvement of an iron carbene species in the mechanism of octene epoxidation by P. oleovorans monooxygenase. © 1990, American Chemical Society. All rights reserved.