American Chemical Society
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Stereochemistry of Epoxidation of Some Caryophyllenols

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journal contribution
posted on 1997-04-04, 00:00 authored by Isidro G. Collado, James R. Hanson, Peter B. Hitchcock, Antonio J. Macías-Sánchez
Epoxidation of the caryophyllene allylic alcohols 35 by tert-butyl hydroperoxide/vanadyl acetylacetonate afforded the epoxides 6a, 7, and 8, respectively. The tetracyanoethylene-catalyzed solvolysis shed some light on the stereochemistry of epoxidation. Formation of trans epoxides by syn epoxidation is a consequence of the conformational flexibility of the nine-membered ring, which places the alcohol at C-5 close to the α-face of the endo-alkene in 4 and close to the β-face in 3 and 5.