Regioselective oxyfunctionalization of unactivated carbons in steroids by a model of cytochrome P-450: osmiumporphyrin complex/tert-butyl hydroperoxide system.
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.
Iida
Takashi
T
Department of Chemistry, College of Humanities and Sciences, Nihon University, Sakurajousui, Setagaya, Tokyo 156-8550, Japan. takaiida@chs.nihon-u.ac.jp
Ogawa
Shoujiro
S
Hosoi
Keiji
K
Makino
Mitsuko
M
Fujimoto
Yasuo
Y
Goto
Takaaki
T
Mano
Nariyasu
N
Goto
Junichi
J
Hofmann
Alan F
AF
D002244:Carbon; D002757:Cholanes / Q000737:chemistry / Q000378:metabolism; D003577:Cytochrome P-450 Enzyme System / Q000737:chemistry / Q000378:metabolism*; D004962:Estranes / Q000737:chemistry / Q000378:metabolism; D006900:Hydroxylation; D008954:Models, Biological; D008956:Models, Chemical; D009942:Organometallic Compounds / Q000737:chemistry / Q000378:metabolism*; D009992:Osmium; D010084:Oxidation-Reduction; D011166:Porphyrins; D011278:Pregnanes / Q000737:chemistry / Q000378:metabolism; D013256:Steroids / Q000737:chemistry / Q000378:metabolism*; D020122:tert-Butylhydroperoxide / Q000737:chemistry / Q000378:metabolism*
D002757:Cholanes; D004962:Estranes; D009942:Organometallic Compounds; D011166:Porphyrins; D011278:Pregnanes; D013256:Steroids; D009992:Osmium; D002244:Carbon; D003577:Cytochrome P-450 Enzyme System; D020122:tert-Butylhydroperoxide