ETUDE DU CARACTERE NUCLEOPHILE DES RADICAUX LORS DE LA REACTION DE TRANSFERT SUR LA LIAISON O-O DES PERACIDES

Article abstract of DOI:10.1016/0040-4020(80)80056-1

Peracids RCO3H yield free radicals R^. which react either with the peracid or with solvent giving the alcohol ROH and the hydrocarbon RH.The nucleophilic character of the free radicals was modified either by substitution of the carbon bearing the odd electron by inductive groups or by changing the free radical hybridation by the means of blocked structures such as cyclic or bicyclic free radicals.For each R^., the measurement of the ratio ROH/RH establishes a reactivity scale for R^. with the peracid O-O bond.This reactivity does not depend on free radical stability but depends strongly on nucleophilic character.A primary free radical is less reactive than a secondary one, and is much less reactive than a tertiary one.A bridgehead free radical as the bicyclo<2.2.1>heptyle-1 does not react with the peracid.These results are interpreted to indicate a transition state with charge transfer (polar effect), the peracid being electrophilic and the free radical nucleophilic; PMO theory is discussed.