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A facile metal-free synthesis of 2-aminothiophene derivatives by the reaction of 2-ynals with thioamides in alcohols has been developed. This transformation allows the assembly of 2-aminothienyl ether derivatives via a well-designed aldol condensation/regioselective intramolecular cyclization/conjugate addition cascade reaction and provides a straightforward synthetic protocol for constructing 2,3,5-trisubstituted 2-aminothiophenes.

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A facile and direct synthetic method was developed for the construction of structurally important 2-aminothiophenes in moderate to excellent yields (up to 91%), via Cu(II)-catalyzed addition/oxidative cyclization of readily available thioamides with alkynoates under an air atmosphere.