<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>Various title compounds (V) and (IX) are obtained by thermolysis of alkyl(aryl) 3‐azidothieno[2, 3‐b]pyridine‐2‐carboxylates containing an aryl or heteroaryl substituent at position C‐4 of the thienopyridine core (IV) and (VIII).</p> </abstract>