Domino CN Coupling/Annulation versusCN Coupling/ Hydroamination of 2‐Alkynyl‐3‐bromobenzothiophenes and 2‐Alkynyl‐3‐bromothiophenes. Highly Efficient Synthesis of Benzothieno[3,2‐b]quinolines and Thieno[3,2‐b]pyrroles

While the palladium‐catalyzed reaction of 2‐alkynyl‐3‐bromothiophenes with anilines afforded thienopyrroles by a domino CN coupling/hydroamination process, the reaction of 2‐alkynyl‐3‐bromobenzothiophenes with anilines resulted, under identical conditions, in the formation of benzothienoquinolines by a domino CN coupling/annulation process. The electronic character of the aniline also has an influence on the product distribution.