Regioselective oxyfunctionalization of unactivated carbons in steroids by a model of cytochrome P-450: osmiumporphyrin complex/tert-butyl hydroperoxide system

Takashi Iida; Shoujiro Ogawa; Keiji Hosoi; Mitsuko Makino; Yasuo Fujimoto; Takaaki Goto; Nariyasu Mano; Junichi Goto; Alan F Hofmann

doi:10.1021/jo061800g

Regioselective oxyfunctionalization of unactivated carbons in steroids by a model of cytochrome P-450: osmiumporphyrin complex/tert-butyl hydroperoxide system

J Org Chem. 2007 Feb 2;72(3):823-30. doi: 10.1021/jo061800g.

Authors

Takashi Iida¹, Shoujiro Ogawa, Keiji Hosoi, Mitsuko Makino, Yasuo Fujimoto, Takaaki Goto, Nariyasu Mano, Junichi Goto, Alan F Hofmann

Affiliation

¹ Department of Chemistry, College of Humanities and Sciences, Nihon University, Sakurajousui, Setagaya, Tokyo 156-8550, Japan. takaiida@chs.nihon-u.ac.jp

PMID: 17253801
DOI: 10.1021/jo061800g

Abstract

tert-Butyl hydroperoxide catalyzed by (5,10,15,20-tetramesitylporphyrinate) osmium(II) carbonyl [Os(TMP)CO] complex was found to be a highly efficient versatile oxidant for C-H carbons in steroid substrates. When reacted with representative steroids with an estrane, pregnane, 5beta-cholane, or 5alpha-cholestane structure, regioselective oxyfunctionalization and/or oxidative degradation occurred to give a variety of novel and uncommon derivatives in one step.

MeSH terms

Carbon*
Cholanes / chemistry
Cholanes / metabolism
Cytochrome P-450 Enzyme System / chemistry
Cytochrome P-450 Enzyme System / metabolism*
Estranes / chemistry
Estranes / metabolism
Hydroxylation
Models, Biological
Models, Chemical
Organometallic Compounds / chemistry
Organometallic Compounds / metabolism*
Osmium*
Oxidation-Reduction
Porphyrins*
Pregnanes / chemistry
Pregnanes / metabolism
Steroids / chemistry
Steroids / metabolism*
tert-Butylhydroperoxide / chemistry
tert-Butylhydroperoxide / metabolism*

Substances

Cholanes
Estranes
Organometallic Compounds
Porphyrins
Pregnanes
Steroids
Osmium
Carbon
Cytochrome P-450 Enzyme System
tert-Butylhydroperoxide