Biomimetic oxidation of unactivated carbons in steroids by a model of cytochrome P-450, oxorutheniumporphyrinate complex

被引：15

作者：

Iida, T ^{[1
]}

Ogawa, S

Miyata, S

Goto, T

Mano, N

Goto, J

Nambara, T

机构：

[1] Nihon Univ, Coll Humanities & Sci, Dept Chem, Tokyo 1568550, Japan

[2] Tohoku Univ, Grad Sch Pharmaceut Sci, Sendai, Miyagi 9808578, Japan

来源：

LIPIDS | 2004年 / 39卷 / 09期

关键词：

D O I：

10.1007/s11745-004-1309-0

中图分类号：

Q5 [生物化学]; Q7 [分子生物学];

学科分类号：

071010 ; 081704 ;

摘要：

Biomimetic oxidation of unactivated carbons for structurally different steroids was studied with a model of cytochrome P-450, oxorutheniumporphyrinate complex, which is generated in situ by 2,6-dichloropyridine N-oxide as an oxygen donor and (5,10,1 5,20-tetramesitylporphyrinate) ruthenium(II) carbonyl complex and HBr as catalysts. The O-insertion positions depended significantly on specific structural features of the substrates to give novel and remote-oxygenated steroids in one step. The electrophilic oxorutheniumporphyrinate attacked predominantly allylic and benzylic beta-carbons adjacent to a pi-bond and/or less hindered, electron-rich tert-methine carbons in the substrates to give regio- and stereoselectively the corresponding oxo and/or hydroxy derivatives.

引用

页码：873 / 880

页数：8

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