Symmetrical and unsymmetrical heteroacenes containing thiophene and pyrrole rings were synthesized. The unsymmetrical heteroacene was synthesized in two steps involving an unexpected palladium catalyzed amination of alkyl or aryl amines with benzo [b] thiophene followed by a copper catalyzed coupling. The symmetrical heteroacene was obtained by a palladium catalyzed amination reaction and also by a copper catalyzed amidation ...