Aromatic Metamorphosis of Thiophenes by Means of Desulfurative Dilithiation. Issue 14 (5th February 2021)

• Record Type: Journal Article
• Authors: Kaga, Atsushi; Iida, Hirokazu; Tsuchiya, Shun; Saito, Hayate; Nakano, Koji; Yorimitsu, Hideki
• Is Part Of: Chemistry. Volume 27:Issue 14(2021)
• Page Start: 4567
• Page End: 4572
• Publication Date: 2021-02-05
• Subjects: desulfurization -- dianion -- heterole -- lithium metal -- thiophene; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.202005223
• Languages: English
• ISSNs: 0947-6539

Abstract

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. Abstract : Desulfurative dilithiation of thiophenes and benzo‐fused derivatives using lithium metal has been developed for the efficient generation of multi‐substituted 1, 4‐dilithium compounds. The resulting dianions are key intermediates for the synthesis of diverse heteroles. This protocol also enables the desulfurative construction of aromatic rings from thiophene derivatives in a one‐pot manner.