For cyclic allylic alcohols, greater selectivity is seen when the alcohol was locked in the pseudo equatorial position rather than the pseudo axial position. However, it was found that for metal catalyzed systems such as those based on vanadium, reaction rates were accelerated when the hydroxyl group was in the axial position by a factor of 34. Substrates which were locked in the pseudo equatorial position were shown to undergo oxidation to form the ene-one. In both cases of vanadium catalyzed epoxidations, the epoxidzed product showed excellent selectivity for the syn diastereomer.