Two methyl 3-aminothieno [3, 2-b] pyridine-2-carboxylates were prepared from 3-fluoro or 3- nitropicolinonitriles and methyl thioglycolate in DMF/KOH (aq). From the unsubstituted precursor in the pyridine ring, di (hetero) arylamines were obtained by C–N Buchwald– Hartwig coupling with bromonitrobenzenes and with 2-bromopyridine. In the latter case a tetracyclic compound was formed by intramolecular cyclization. Using a brominated ...