Synthesis of cyclic peroxides by chemo- and regioselective peroxidation of dienes with Co(II)/O-2/Et3SiH

In the competitive peroxidation of mixtures of two alkenes with Co(II)/O-2/Et3SiH, it was found that the relative reactivities of the alkene substrates are influenced by three major factors:. (1) relative stability of the intermediate carbon-centered radical formed by the reaction of the alkene with...

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Bibliographic Details
Published inJournal of organic chemistry Vol. 70; no. 1; pp. 251 - 260
Main Authors Tokuyasu, T, Kunikawa, S, McCullough, KJ, Masuyama, A, Nojima, M
Format Journal Article
LanguageEnglish
Published WASHINGTON Amer Chemical Soc 07.01.2005
Subjects
Chemistry
Chemistry, Organic
Physical Sciences
Science & Technology
MECHANISM
UNSATURATED HYDROPEROXIDES
HYDROGEN-TRANSFER
ARTEMISININ DERIVATIVES
RATE CONSTANTS
YINGZHAOSU-C
STEREOCHEMISTRY
PEROXYL RADICAL CYCLIZATION
RING-CLOSURE
MOLECULAR-OXYGEN
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Summary:In the competitive peroxidation of mixtures of two alkenes with Co(II)/O-2/Et3SiH, it was found that the relative reactivities of the alkene substrates are influenced by three major factors:. (1) relative stability of the intermediate carbon-centered radical formed by the reaction of the alkene with HCo(III) complex, (2) steric effects around the C=C double bond, and (3) electronic factors associated with the C=C double bond. Consistent with results from simple alkenes, the chemo-and regioselective peroxidation of dienes was also realized. Depending on the diene structure, the product included not only the expected acyclic unsaturated triethylsilyl peroxides but also 1,2-dioxolane and 1,2-dioxane derivatives via intramolecular cyclization of the unsaturated peroxy radical intermediates.
ISSN:0022-3263
DOI:10.1021/jo048359j