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The substitution of protonated heteroaromatic bases by nucleophilic carbon‐centered radicals has been developed as one of the most general reactions in the heterocyclic series; its great interest results from the fact that it reproduces most of the numerous aspects of the Friedel‐Crafts aromatic substitution, but with opposite reactivity and selectivity. The most recent developments, concerning the generation of free radicals by iodine and hydrogen abstraction and decarboxylation of carboxylic acids are particularly discussed. Some processes of high synthetic value were designed on the basis of the kinetic and thermodynamic features of all the elementary steps involved in complex but selective chain processes. New general procedures for the monosubstitution in the homolytic alkylation and acylation are reported and discussed.