The mechanisms of the rearrangements of allylic hydroperoxides

Abstract

The suprafacial rearrangement of 3β-hydroxy-5α-hydroperoxy-Δ6-cholestene to the 7α-hydroperoxy-Δ5 isomer does not involve exchange of O2 with the atmosphere, suggesting that it proceeds by a non-dissociative mechanism; on the other hand, the slower subsequent rearrangement of the 7α-Δ5-hydroperoxide to the 7β-Δ5-hydroperoxide is susceptible to exchange, and follows a dissociative mechanism.