Polar Effects in Free Radical Reactions. Induced Decompositions of Peroxo Compounds in the Substitution of Heteroaromatic Bases by Nucleophilic Radicals

Article abstract of DOI:10.1021/ja00335a048

The decomposition of benzoyl and lauroyl peroxides and potassium peroxydisulfate in various solvents leads to the selective substitution at position 2 of protonated lepidine by the nucleophilic free generated in the reactions (^.CH2OH, dioxanyl, ^.CON(CH3)2, CHON(CH3)CH2^., (CH3)2C^.H, cyclohexyl, and n-C11H23^.).The remarkable induced decomposition of the peroxides, observed in all cases, is rationalized by the intermediacy of a strongly nucleophilic pyridinyl radical, which undergoes a ready and selective rearomatization and consequently contributes to the great synthetic interest of the homolytic substitution of protonated heteroaromatic bases by nucleophilic free radicals.