Enzymatic oxygenation of sulfides with cytochrome P-450 from rabbit liver. Stereochemistry of sulfoxide formation.
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概要
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Stereochemistry of enzymatic oxygenations of various diaryl, dialkyl and aryl alkyl sulfides to the corresponding sulfoxides with hepatic microsomes obtained from phenobarbital pretreated rabbit was investigated in comparison with those of nonenzymatic oxidations. Relative reactivity of the sulfides in the enzymatic oxygenation, based on the yields of the sulfoxides and the amount of oxygen absorption, depends upon the steric demand of the substituent in the oxygenation of 2-substituted thiochroman derivatives. However, such a trend was not observed in the enzymatic oxygenations of various acyclic sulfides. A substantial asymmetric induction on the sulfur atom was always observed (<I>e.g.</I>, 54% <I>e.e.</I> for benzyl <I>t</I>-butyl sulfide). Formation of the sulfoxide with <I>R</I>-configuration predominated over that with <I>S</I>-configuration. The enzymatic oxygenation of all the unsymmetrical sulfides examined proceeded <I>via</I> the same steric course. Diastereomeric ratios of the sulfoxides formed in the enzymatic oxygenations of various racemic sulfides bearing alkyl substituents at α-position are markedly favoured more for the trans isomers than for the cis ones, while the ratio was nearly fifty-fifty in the nonenzymatic oxidations with both MCPBA and NaIO<SUB>4</SUB>. These results suggest that the enzymatic oxygenation takes place at the less hindered side of the sulfide. Both enzymatic and nonenzymatic oxidations of rigid six-membered cyclic sulfides, <I>trans</I>-thiadecalins and 4-(<I>p</I>-chlorophenyl)thiane, similarly occurred at the less hindered side to give mainly equatorial sulfoxides. The yields of the four stereoisomeric sulfoxides were nicely determined in the enzymatic oxygenation of racemic 2-methyl-2,3-dihydrobenzothiophene to elucidate the steric course of the oxygenation. Dependency of this microsomal oxygenation upon cytochrome P-450 enzyme was proved by several inhibition experiments and also by the identical stereochemical results of the oxygenation of a few selected sulfides to those with a reconstituted system with purified cytochrome P-450 and co-factors.
- 公益社団法人 日本化学会の論文
著者
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Takata Toshikazu
Department Of Applied Chemistry Graduate School Of Engineering Osaka Prefecture University
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Fujimori Ken
Department Of Anatomy School Of Medicine Faculty Of Pharmaceutical Sciences Tokushima University
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Kim Yong
Department And Research Institute Of Rehabilitation Medicine Yonsei University College Of Medicine
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Oae Shigeru
Deparment of Applied Chemistry Faculty of Engineering Osaka City University
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Yamazaki Mayumi
Department of Chemistry, University of Tsukuba
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Iyanagi Takashi
Devision of Biochemistry, School of Medicine, University of Tsukuba
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