Organocatalytic stereoselective construction of polycyclic benzo[]thiophenes from 2-aminobenzo[]thiophenes and alkynyl-substituted enones

• Published in: New journal of chemistry Vol. 47; no. 3; pp. 14515 - 14519
• Main Authors: Niu, Cheng, Zheng, Yao, Du, Da-Ming
• Format: Journal Article
• Language: English
• Published: CAMBRIDGE Royal Soc Chemistry 31.07.2023; Royal Society of Chemistry
• Subjects: Benzothiophene; Chemical reactions; Chemistry; Chemistry, Multidisciplinary; Physical Sciences; Science & Technology; Stereoselectivity; Sulfonamides; Thiophenes; ANNULATIONS; BAYLIS-HILLMAN CARBONATES; SULFUR; FURANS; CONJUGATE ADDITION
• ISSN: 1144-0546; 1369-9261
• DOI: 10.1039/d3nj02798h

A highly efficient protocol for stereoselective synthesis of novel polycyclic benzo[ b ]thiophene derivatives was developed. Using quinine-derived bifunctional thiourea (5 mol%) as a catalyst, asymmetric [3+3] annulation of N -(benzo[ b ]thiophen-2-yl)-sulfonamide with 2-alkynyl cycloenone could provide dihydrobenzo[4,5]thieno[2,3- b ]pyridine derivatives in moderate to good yields (up to 93%) with mostly excellent enantioselectivities (up to 97% ee) under mild conditions. In addition, large-scale experiments and derivatizations were explored. In particular, the target product in large-scale experiments could be easily purified by filtration and the filtrated product showed >99% ee. Bifunctional thiourea-catalyzed asymmetric [3+3] annulation of 2-aminobenzothiophenes with alkynyl-substituted enones for enantioselective synthesis of polycyclic benzothiophenes with high stereoselectivities was developed.