title: The mechanism of oxidation of allylic alcohols to alpha,beta-unsaturated ketones by cytochrome P450.
abstract: The oxidation of cyclohex-2-en-1-ol, a simple model substrate for allylic alcohols, is catalyzed by several P450 isoenzymes and leads exclusively to cyclohex-2-en-1-one. No double bond epoxidation or C(4) hydroxylation have been observed. The large primary kinetic isotope effect measured using [2H]-1-cyclohex-2-en-1-ol is consistent with an at least partially rate limiting breaking of the C(1)-H bond. The mass spectrometric analysis of cyclohex-2-en-1-one obtained from [18O]cyclohex-2-en-1-ol has established that a gem-diol intermediate is involved, even if a dual hydrogen abstraction pathway may contribute to the reaction.
authors.affiliation: Dipartimento di Chimica Bioorganica, Università di Pisa, Italy.
authors.forename: G
authors.initials: G
authors.lastname: Bellucci
authors.forename: C
authors.initials: C
authors.lastname: Chiappe
authors.forename: L
authors.initials: L
authors.lastname: Pucci
authors.forename: P G
authors.initials: PG
authors.lastname: Gervasi
mesh_terms: D000498:Allyl Compounds / Q000378:metabolism*; D000818:Animals; D003577:Cytochrome P-450 Enzyme System / Q000378:metabolism*; D003903:Deuterium; D004790:Enzyme Induction / Q000187:drug effects; D066298:In Vitro Techniques; D007659:Ketones / Q000378:metabolism*; D007700:Kinetics; D008297:Male; D013058:Mass Spectrometry; D008862:Microsomes, Liver / Q000201:enzymology; D010084:Oxidation-Reduction; D010103:Oxygen Isotopes; D051381:Rats; D017207:Rats, Sprague-Dawley
chemical_list: D000498:Allyl Compounds; D007659:Ketones; D010103:Oxygen Isotopes; D003577:Cytochrome P-450 Enzyme System; D003903:Deuterium