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Quantum mechanical study of putative intermediates in adduct formation by the suicide substrate ethylene with cytochrome P‐450
Author(s) -
Collins J. R.,
Luke B. T.,
Loew G. H.
Publication year - 2009
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.560300815
Subject(s) - adduct , chemistry , porphyrin , cytochrome , ethylene , photochemistry , epoxide , substrate (aquarium) , reactive intermediate , pyrrole , stereochemistry , catalysis , organic chemistry , enzyme , oceanography , geology
We report INDO calculations on putative intermediates in the oxidative metabolism of ethylene by cytochrome P‐450 leading to either the epoxide or the formation of an adduct at the pyrrole nitrogen of the porphyrin. We also report the characterization of a ferryl model which has been postulated to be the active oxygen state involved in oxidation reactions involving cytochrome P‐450. Our results suggest that adduct formation proceeds via a radical process which leaves the oxygen bound to the iron forming a five‐membered cyclic structure. The possibility of an intermediate which could lead to either the epoxide or the N ‐alkylated porphyrin is discussed.