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

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Lipids

Abstract

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 (5,10,15,20-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 β-carbons adjacent to a π-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.

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Abbreviations

APCI:

atmospheric pressure CI

DCP:

2,6-dichloropyridine

EI:

electron ionization

ESI:

electrospray ionization

Fr:

fraction

HR-MS:

high-resolution MS

LR-MS:

low-resolution MS

MPLC:

medium-pressure LC

NIM:

negative ion mode

PIM:

positive ion mode

SC:

side chain

TMP:

tetramesitylporphyrinate

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Authors and Affiliations

  1. Department of Chemistry, College of Humanities and Sciences, Nihon University, Sakurajousui, 156-8550, Setagaya, Tokyo, Japan

    Takashi Iida, Shoujiro Ogawa & Shouhei Miyata

  2. Graduate School of Pharmaceutical Sciences, Tohoku University, Aobayama, 980-8578, Sendai, Japan

    Takaaki Goto, Nariyasu Mano, Junichi Goto & Toshio Nambara

Authors
  1. Takashi Iida
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  2. Shoujiro Ogawa
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  3. Shouhei Miyata
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  4. Takaaki Goto
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  5. Nariyasu Mano
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  6. Junichi Goto
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  7. Toshio Nambara
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Correspondence to Takashi Iida.

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Iida, T., Ogawa, S., Miyata, S. et al. Biomimetic oxidation of unactivated carbons in steroids by a model of cytochrome P-450, oxorutheniumporphyrinate complex. Lipids 39, 873–880 (2004). https://doi.org/10.1007/s11745-004-1309-0

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  • DOI: https://doi.org/10.1007/s11745-004-1309-0

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