Tetraacetylethylene (1), and cis‐diacetylethylene (4) reacted under mild conditions with 3‐amino‐2‐butenoic acid methyl ester (6), benzene‐1,2‐diamine and naphthalene‐2,3‐diamine to give polysubstituted pyrroles, 2,3‐disubstituted quinoxalines and 2,3‐disubstituted benzo[g]quinoxalines respectively. Some aspects of the reactions mechanisms are discussed.