Polyfunctional peroxides from tert-butyl hydroperoxide-loaded autoxidations of polyunsaturated substrates and an assessment of the rate constants for allylic peroxyl radical rearrangements and peroxyl radical ring closures

Abstract

Using the recently-disclosed tert-butyl hydroperoxide-loaded autoxidation method, cis-2,6-dimethyl-2,6-octadiene and trans-5-methyl-1,5,9-decatriene have been converted into hydroperoxy-1,2-dioxanes and hydroperoxy-1,2-dioxolanes: the product ratios from these, and other, reactions permit an assessment of the relative magnitudes of allylic peroxyl radical rearrangements and of peroxyl radical cyclizations.