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

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dc.contributor.authorBack, Thomas George
dc.contributor.authorSands, Kai N
dc.contributor.authorMendoza Rengifo, Emerita
dc.contributor.authorGeorge, Graham N
dc.contributor.authorPickering, Ingrid J
dc.contributor.authorGelfand, Benjamin S
dc.date.accessioned2020-01-02T16:40:21Z
dc.date.available2020-01-02T16:40:21Z
dc.date.issued2019-12-24
dc.description.abstractBenzeneperoxyseleninic 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, 77 Se NMR spectroscopy, and 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.en_US
dc.identifier.doihttp://dx.doi.org/10.1002/anie.201913566en_US
dc.identifier.urihttp://hdl.handle.net/1880/111401
dc.identifier.urihttps://doi.org/10.11575/PRISM/46092
dc.language.isoengen_US
dc.publisher.facultyScienceen_US
dc.publisher.institutionUniversity of Calgaryen_US
dc.rightsUnless otherwise indicated, this material is protected by copyright and has been made available with authorization from the copyright owner. You may use this material in any way that is permitted by the Copyright Act or through licensing that has been assigned to the document. For uses that are not allowable under copyright legislation or licensing, you are required to seek permission.en_US
dc.subjectbenzeneperoxyseleninic aciden_US
dc.subjectbenzeneperoxyselenonic aciden_US
dc.subjectepoxidationen_US
dc.subjectoxidationen_US
dc.subjectperoxidesen_US
dc.titleThe Unexpected Role of Se(VI) Species in Epoxidations with Benzeneseleninic Acid and Hydrogen Peroxideen_US
dc.typejournal articleen_US
dc.typeacceptedVersionen_US
dc.typejournal articleen_US
dc.typeacceptedVersionen_US
ucalgary.item.requestcopytrueen_US
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