posted on 1997-04-04, 00:00authored byIsidro G. Collado, James R. Hanson, Peter B. Hitchcock, Antonio J. Macías-Sánchez
Epoxidation of the caryophyllene allylic alcohols
3−5 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.