Oxygenation of Substituted Vinylcyclopropanes: Preparative and Mechanistic Studies

1-Vinylcyclopropanes bearing phenyl, vinyl, or ester substituents at C(2) of the cyclopropyl ring or alkyl groups at C(1) of the vinyl moiety were subjected to phenylthio or phenylseleno radical catalyzed oxygenation to furnish the corresponding substituted 1,2-dioxolane products. A self-consistent hypothesis was developed which describes the gross features of this multistep transformation. The mechanistic basis for stereochemical issues, including 1,2 relative asymmetric induction upon oxygen addition and stereochemistry upon cyclization of a putative 5-hexenylperoxy radical, were probed through substituent effects and deuterium-labeling studies. Reduction of the 1,2-dioxolane products afforded functionalized 1,3-diol derivatives.