Oxymetallation. Part 24. Preparation of cyclic peroxides by cycloperoxymercuriation of unsaturated hydroperoxides

Article abstract of DOI:10.1016/S0040-4020(01)86350-X

Seventeen unsaturated hydroperoxides have been converted by treatment with mercury(II) acetate and/or mercury(II) nitrate into nineteen new mercuriated cyclic peroxides and by subsequent demercuriation with alkaline sodium borohydride, six new mercury-free peroxides have been isolated. The results greatly extend the range of such reactions and provide information about the stereoselectivities and relative ease of several different modes of cycloperoxymercuriation. It is suggested that the reactions with mercury(II) acetate are kinetically controlled whereas those with mercury(II) nitrate show a component of thermodynamic control of product distribution.