Remote functionalisation by ferrous ion-cupric ion induced decomposition of alkyl hydroperoxides

By decomposition of alkyl hydroperoxides 1-8 with ferrous sulfate-cupric acetate reagent, intramolecular functionalisation of remote non-activated C atom takes place and unsaturated alcohols with double bond mainly at δ-position are obtained. The reaction proceeds involving the corresponding alkoxy radical 9 and δ-carbon radical 10 as intermediates. One-electron oxidative interception of δ-carbon radical by cupric acetate does not involve the corresponding carbonium ion; instead, the alkyl-copper intermediate 11 is formed and by elimination affords olefinic alcohols. The isotope effect for this elimination process was found to be kh/kd=6.1. © 1979