The oxidation of cyclohex-2-en-l-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 [H-2]-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 [O-18]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.
The mechanism of oxidation of allylic alcohols to alpha,beta-unsaturated ketones by cytochrome p450
CHIAPPE, CINZIA;
1996-01-01
Abstract
The oxidation of cyclohex-2-en-l-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 [H-2]-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 [O-18]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.File in questo prodotto:
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