Light-mediated transformations of olefins into alcohols: reactions of hydroxyl radicals with cycloalkenes

Reactions of hydroxyl radicals, generated by photodecomposition of hydrogen peroxide in acetonitrile, with a wide variety of cycloalkenes have been examined. The results show that the major reaction is the addition of hydroxyl radicals to the less substituted end of the double bond, furnishing the secondary alcohols. The reactivity pattern and the observed regio- and stereoselectivity clearly reveal that the steric parameters associated with the substrates play a dominant role in directing the addition reactions. More importantly, this study led to the development of a new methodology for the facile conversions of olefins essentially into secondary alcohols, and includes a few examples which demonstrate the potential of the method.