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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 international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201504013
Subject(s) - chemistry , carbenoid , sulfanyl , intramolecular force , moiety , carbene , sulfur , nucleophile , medicinal chemistry , enamine , thioester , diphenylacetylene , ring (chemistry) , rhodium , 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.