TY - JOUR
T1 - Biomimetic oxidation of unactivated carbons in steroids by a model of cytochrome P-450, oxorutheniumporphyrinate complex
AU - Iida, Takashi
AU - Ogawa, Shoujiro
AU - Miyata, Shouhei
AU - Goto, Takaaki
AU - Mano, Nariyasu
AU - Goto, Junichi
AU - Nambara, Toshio
N1 - Funding Information:
This work was supported by a Grant-in-Aid for Scientific Research from the Ministry of Education, Sciences, Sports and Culture of Japan and by Nihon University Multidisciplinary Research Grant for 2004.
PY - 2004/9
Y1 - 2004/9
N2 - 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.
AB - 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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U2 - 10.1007/s11745-004-1309-0
DO - 10.1007/s11745-004-1309-0
M3 - Article
C2 - 15669763
AN - SCOPUS:11144351962
VL - 39
SP - 873
EP - 880
JO - Lipids
JF - Lipids
SN - 0024-4201
IS - 9
ER -