THE OXYGENATION OF VINYLCYCLOPROPANES AS AN ENTRY INTO STEREOSELECTIVE 1,3-DIOL SYNTHESIS

Chalcogen radical catalyzed addition of molecular oxygen (O-3(2)) across the carbon-carbon bond of suitably activated vinylcyclopropanes affords 1,2-dioxolane products in moderate to excellent yield. Stereoselective preparation of either the syn or the anti dioxolane ring can be achieved by carefully balancing the steric and electronic characteristics of the vinylcyclopropane substituents. A mechanistic rationale for this complex multi-step transformation, including a discussion of the structural basis for product diastereoselectivity, is offered. Reductive cleavage of the 1,2-dioxolane ring's oxygen-oxygen bond provides the target syn or anti 1,3-diols in good yield.