On the Mode of Epoxidation by the Tetraphenylporphinatoiron (III)-Iodosylbenzene System

Epoxidation of cholesteryl acetate by a nonradical reagent system such as m-chloroperbenzoic acid, Mo (CO)6-'BuOOH, or Fe (ClO4)3-H2O2 was highly α-stereoselective. In contrast, a radical reagent system such as Fe (acac)3-'BuOOH, KO2-'BuBr, or biacetyl-O2-hv, showed high β-selectivity...

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Published inChemical & pharmaceutical bulletin Vol. 33; no. 11; pp. 4749 - 4754
Main Authors MUTO, TOSHIKI, UMEHARA, JUNKO, MASUMORI, HIROAKI, MIURA, TOSHIAKI, KIMURA, MICHIYA
Format Journal Article
LanguageEnglish
Published Tokyo The Pharmaceutical Society of Japan 1985
Maruzen
Japan Science and Technology Agency
Subjects
Chemistry
Exact sciences and technology
iodosylbenzene
Kinetics and mechanisms
Organic chemistry
Reactivity and mechanisms
Steroid
Hydrocarbon
Cytochrome P450
Molybdenum Carbonyl
Transition metal Complexes
Hydrogen Peroxides
Stereoselectivity
Iron III Complexes
Radical mechanism
Epoxidation
Benzenic compound
Models
Metalloporphyrin
Iron III Perchlorates
Ethylenic compound
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Summary:Epoxidation of cholesteryl acetate by a nonradical reagent system such as m-chloroperbenzoic acid, Mo (CO)6-'BuOOH, or Fe (ClO4)3-H2O2 was highly α-stereoselective. In contrast, a radical reagent system such as Fe (acac)3-'BuOOH, KO2-'BuBr, or biacetyl-O2-hv, showed high β-selectivity. The stereoselectivity in the epoxidation of cholesteryl acetate seems, therefore, to be a useful indication of the mode of reaction. On this basis, epoxidation may occur through a radical process in the tetraphenylporphinatoiron (III) chloride-iodosylbenzene system. Earlier studies with stilbene had failed to clarify the mechanism in this system.
ISSN:0009-2363
1347-5223
DOI:10.1248/cpb.33.4749