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 …