Synthesis of cyclic peroxides by chemo- and regioselective peroxidation of dienes with Co(II)/O2/Et3SiH

Takahiro Tokuyasu, Shigeki Kunikawa, Kevin J. McCullough, Araki Masuyama, Masatomo Nojima

Research output: Contribution to journalArticle

58 Citations (Scopus)

Abstract

(Chemical Equation Presented). In the competitive peroxidation of mixtures of two alkenes with Co(II)/O2/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.

Original languageEnglish
Pages (from-to)251-260
Number of pages10
JournalJournal of Organic Chemistry
Volume70
Issue number1
DOIs
Publication statusPublished - 7 Jan 2005

Fingerprint Dive into the research topics of 'Synthesis of cyclic peroxides by chemo- and regioselective peroxidation of dienes with Co(II)/O<sub>2</sub>/Et<sub>3</sub>SiH'. Together they form a unique fingerprint.

Cite this