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A Reaction of Triazoles with Thioesters to Produce β‐Sulfanyl Enamides by Insertion of an Enamine Moiety into the Sulfur–Carbonyl Bond
Author(s) -
Miura Tomoya,
Fujimoto Yoshikazu,
Funakoshi Yuuta,
Murakami Masahiro
Publication year - 2015
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201504013
Subject(s) - chemistry , carbenoid , sulfanyl , intramolecular force , thioester , carbene , moiety , enamine , sulfur , nucleophile , medicinal chemistry , nucleophilic addition , rhodium , insertion reaction , stereochemistry , catalysis , organic chemistry , enzyme
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.