A Reaction of Triazoles with Thioesters to Produce β-Sulfanyl Enamides by Insertion of an Enamine Moiety into the Sulfur-Carbonyl Bond

• Published in: Angewandte Chemie (International ed.) Vol. 54; no. 34; pp. 9967 - 9970
• Main Authors: Miura, Tomoya, Fujimoto, Yoshikazu, Funakoshi, Yuuta, Murakami, Masahiro
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 17.08.2015; WILEY‐VCH Verlag; Wiley; Wiley Subscription Services, Inc
• Edition: International ed. in English
• Subjects: Amides; carbenoids; Carbonyl compounds; Carbonyls; Catalysts; Chemistry; Chemistry, Multidisciplinary; copper; Formations; heterocycles; Migration; Nitrogen; Nuclei; Physical Sciences; Rhodium; Science & Technology; Stereoselectivity; Sulfur; Thioesters; Triazoles; RHODIUM(II) AZAVINYL CARBENES; TERMINAL ALKYNES; CONTROLLING SELECTIVITY; 1-SULFONYL-1,2,3-TRIAZOLES; N-SULFONYL-1,2,3-TRIAZOLES; REARRANGEMENT; CYCLOADDITION; SULFONYL AZIDES; heterocycles; CATALYZED TRANSANNULATION; carbenoids; copper; sulfur; METAL; rhodium
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201504013

N‐Sulfonyl‐1,2,3‐triazoles react with thioesters in the presence of a rhodium(II) catalyst to produce β‐sulfanyl enamides in a stereoselective manner. The reaction proceeds through generation of an α‐imino rhodium carbene complex, nucleophilic addition of the sulfur atom of a thioester onto the carbenoid carbon atom, and subsequent intramolecular migration of the acyl group from the sulfur atom to the imino nitrogen atom. The method is successfully applied to a ring‐expansion reaction of thiolactones, thus leading to the formation of sulfur‐containing lactams. Expansion project: N‐Sulfonyl‐1,2,3‐triazoles react with thioesters in the presence of a rhodium(II) catalyst to produce β‐sulfanyl enamides in a stereoselective manner. The method is successfully applied to a ring‐expansion reaction of thiolactones (see Scheme; Ts=4‐toluenesulfonyl), thus leading to the formation of sulfur‐containing lactams.