期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 59, 期 11, 页码 4283-4287出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201913566
关键词
benzeneperoxyseleninic acid; benzeneperoxyselenonic acid; epoxidation; oxidation; peroxides
资金
- Natural Sciences and Engineering Research Council of Canada [RGPIN-2019-04373]
- Walpole Island First Nation
- Province of Alberta
- U.S. DOE, Office of Science, OBES [DEAC02-76SF00515]
- DOE OBER
- NIH, NIGMS [P41GM103393]
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 Se-77 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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