The mechanism of oxidation of allylic alcohols to alpha,beta-unsaturated ketones by cytochrome p450

被引：25

作者：

Bellucci, G ^{[1
]}

Chiappe, C ^{[1
]}

Pucci, L ^{[1
]}

Gervasi, PG ^{[1
]}

机构：

[1] CNR,IST MUTAGENESI & DIFFERENZIAMENTO,I-56124 PISA,ITALY

来源：

CHEMICAL RESEARCH IN TOXICOLOGY | 1996年 / 9卷 / 05期

关键词：

D O I：

10.1021/tx9600053

中图分类号：

R914 [药物化学];

学科分类号：

100701 ;

摘要：

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.

引用

页码：871 / 874

页数：4

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