The Smiles rearrangement was successfully applied to 4-hydroxybenzo [b] thiophene furnishing a facile entry to the 4-amino derivative. The rearrangement was extended to 5- methoxy-4-methoxycarbonyl [1] benzothieno [2, 3-b] pyridine obtained via aza-Wittig/ electrocyclization reaction of novel N-(4-methoxybenzothiophen-2-yl) iminomethyldiphenylphosphorane with methyl trans-4-oxo-2-pentenoate. The preparation ...