Mechanisms of enzymatic S-oxygenation of thioanisole derivatives and O-demethylation of anisole derivatives promoted by both microsomes and a reconstituted system with purified cytochrome P-450.

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概要

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• Oxygenations of thioanisole derivatives have been shown to be promoted with phenobarbital induced rabbit liver microsomes. In order to understand the mechanistic details of the oxygenations, a kinetic study on the <I>S</I>-oxygenation promoted by a reconstituted system with purified cytochrome P-450 has been carried out. Log(<I>V</I><SUB>max</SUB>) were correlated with the one electron oxidation potentials of the sulfides (<I>E<SUB>p</SUB></I>). The oxygenation is considered to proceed <I>via</I> one electron transfer from the sulfides to the iron-bound "oxenoid" intermediate of the enzyme. A similar <I>O</I>-demethylation of anisoles has been investigated. In the oxidative <I>O</I>-demethylation of <I>p</I>-methoxy-<I>d</I><SUB>3</SUB>-anisole with rabbit liver microsomes, an intramolecular kinetic isotope effect of 3.4 was observed. Meanwhile, a large isotope effect of 5.1 was observed in the competitive <I>O</I>-demethylation of <I>p</I>-dimethoxybenzene and <I>p</I>-di(methoxy-<I>d</I><SUB>3</SUB>) benzene. In order to clarify the oxidation pathway of <I>O</I>-demethylation with the enzymatic system of cytochrome P-450, the rates of the <I>O</I>-demethylation of <I>p</I>-substituted anisoles have been measured. Unlike the enzymatic oxygenation of sulfides, there was no correlation between the rates of <I>O</I>-demethylation reaction and one electron oxidation potentials of anisoles. These observations suggest that the <I>O</I>-demethylation of anisoles proceeds <I>via</I> the initial hydrogen abstraction with the iron-bound "oxenoid" intermediate of the cytochrome P-450.

• 公益社団法人 日本化学会の論文

著者

• Watanabe Yoshihito

  Department Of Chemistry Graduate School Of Science Nagoya University

• Oae Shigeru

  Deparment of Applied Chemistry Faculty of Engineering Osaka City University

• Iyanagi Takashi

  Division of Biochemistry, School of Medicine, University of Tsukuba

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