Redox-Induced Aromatic Substitution: A Study on Guanidino-Functionalized Aromatics.

Aromatic substitution of redox-active aromatic compounds could be initiated by a preceding redox step. We report on the different reaction pathways of such redox-induced substitution (RIAS) reactions between a redox-active guanidino-functionalized aromatic molecule (GFA) and an amine or guanidine. Oxidation of the GFA leads to an umpolung of the guanidine from a nucleophile to an electrophile and thereby enables addition of the amine or guanidine. Several examples are given, demonstrating the use of redox substitution in synthetic chemistry, e. g. for the convenient synthesis of novel N-heteropolycyclic molecules and unsymmetrically-substituted aromatics.