Collect. Czech. Chem. Commun. 1988, 53, 1549-1567

A contribution to peroxy acid oxidation of α,β-unsaturated ketones and linearly conjugated dienones: Reactions in the cholestane series

Václav Černýa, Miloš Buděšínskýa, Miloš Rybaa and František Turečekb

a Institute of Organic Chemistry and Biochemistry, Czechoslovak Academy of Sciences, 166 10 Prague 6
b The J. Heyrovský Institute of Physical Chemistry and Electrochemistry, Czechoslovak Academy of Sciences, 182 23 Prague 8


Oxidation with 3-chloroperoxybenzoic acid of s-cis α,β-unsaturated ketones IX, XI and s-trans types X, XII was compared. The s-cis ketones show higher reactivity and furnish a higher yield of the corresponding α,β-epoxy ketones than the s-trans ketones. Products of the Baeyer-Villiger reaction are formed only in low yield. The dienone VI is oxidized predominantly to VII thus violating the rule that linear conjugated dienones are epoxidized at the double bond more distant from the carbonyl group; this result is in accord with the behaviour of s-cis α,β-unsaturated ketones. 1H NMR and 13C NMR data of the starting compounds and of the products are reported.