The synthesis of pentasubstituted pyrroles has been described using molecular iodine from 1,3-enynes and amines via a sequential tandem aza-Michael addition, iodocyclization, and oxidative aromatization. The protocol is simple and efficient to afford the target products at ambient conditions.

Domino synthesis of tetrasubstituted thiophenes is described from 1,3-enynes and mercaptoacetaldehyde using DABCO at room temperature via a Michael addition, 5-exo-dig carboannulation, and oxidation sequence under air. The broad substrate scope and mild reaction conditions are significant practical features.

Various tetrasubstituted pyrroles/pyrazoles have been prepared from nitro-substituted 1,3-enynes with aromatic amines/hydrazines via a copper-catalyzed cascade aza-Michael addition, cyclization and aromatization at room temperature. This protocol is also effective for the synthesis of tetrasubstituted pyrazoles in high yields.

A new approach to highly substituted pyrroles by using 1,3‐enynes and primary amines in the presence of excess iodine is developed.

The reaction proceeds via a Michael addition, 5‐exo‐dig carboannulation, and oxidation sequence.