Aromatic Metamorphosis of Thiophenes by Means of Desulfurative Dilithiation

Abstract A new mode of aromatic metamorphosis has been developed, which allows thiophenes and their benzo‐fused derivatives to be converted to a variety of exotic heteroles. This transformation involves 1) the efficient generation of key 1,4‐dianions by means of desulfurative dilithiation with lithium powder and 2) the subsequent trapping of the dianions with heteroatom electrophiles in a one‐pot manner. Via the desulfurative dilithiation, the sulfur atoms of thiophenes are replaced also with a carbon–carbon double bond or a 1,2‐phenylene for the construction of benzene rings.