The photooxygenation of homochiral cyclohexene ketals, which are easily available from 2- cyclohexenone and l-tartrates, affords hydroperoxides and after reduction the corresponding allylic alcohols in good yields and high regioselectivities. This can be rationalized by electronic repulsions in a perepoxide intermediate and provides evidence for unfavorable 1, 3 diaxial interactions with a dioxolane oxygen atom. Only low stereoselectivities were ...