The Unexpected Role of Se VI Species in Epoxidations with Benzeneseleninic Acid and Hydrogen Peroxide

Sands, Kai N.; Mendoza Rengifo, Emerita; George, Graham N.; Pickering, Ingrid J.; Gelfand, Benjamin S.; Back, Thomas G.

doi:10.1002/anie.201913566

Title: The Unexpected Role of Se ^VI Species in Epoxidations with Benzeneseleninic Acid and Hydrogen Peroxide

Journal Article · 30 January 2020 · Angewandte Chemie (International Edition)

DOI: https://doi.org/10.1002/anie.201913566 · OSTI ID:1596164

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Department of Chemistry University of Calgary 2500 University Drive NW Calgary Alberta T2N 1N4 Canada
Department of Geological Sciences University of Saskatchewan 114 Science Place Saskatoon Saskatchewan S7N 5E2 Canada

Abstract Benzeneperoxyseleninic acid has been proposed as the key intermediate in the widely used epoxidation of alkenes with benzeneseleninic acid and hydrogen peroxide. However, it reacts sluggishly with cyclooctene and instead rapidly decomposes in solution to a mixed selenonium–selenonate salt that was identified by X‐ray absorption and ⁷⁷ Se NMR spectroscopy, as well as by single crystal X‐ray diffraction. This process includes a selenoxide elimination of the peroxyseleninic acid with liberation of oxygen and additional redox steps. The salt is relatively stable in the solid state, but generates the corresponding selenonic acid in the presence of hydrogen peroxide. The selenonic acid is inert towards cyclooctene on its own; however, rapid epoxidation occurs when hydrogen peroxide is added. This shows that the selenonic acid must first be activated through further oxidation, presumably to the heretofore unknown benzeneperoxyselenonic acid. The latter is the principal oxidant in this epoxidation.

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Sponsoring Organization:: USDOE

OSTI ID:: 1596164

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Vol. 59 Journal Issue: 11; ISSN 1433-7851

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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Cited by: 17 works

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