5 - Endo ring closures of allylic hydroperoxides: Useful routes to 1,2 - dioxolanes involving strongly stereoselective free radical and polar reactions

Article abstract of DOI:10.1016/S0040-4020(01)92274-4

Intramolecular cyclisation of simple allylic hydroperoxides to give substituted 1,2 - dioxolanes using electrophilic reagents has been investigated. Closure using mercury(II) acetate and electrophilic halogen reagents (NBS, Br₂ Bu^tOC1) occurs by Markovnikov - directed and conformationally strict stereospecificity. Subsequent free - radical reaction of the mercurated dioxolanes involved specific reaction involving reaction from the sterically unprotected face of the intermediate dioxolanyl radical.