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Title: Tosvinyl and besvinyl as protecting groups of imides, azinones, nucleosides, sultams, and lactams. Catalytic conjugate additions to tosylacetylene.
Author: Petit, Elena
Bosch Hereu, Lluís
Font, Joan
Mola Solà, Laura
Costa i Arnau, Anna M.
Vilarrasa i Llorens, Jaume
Keywords: Estereoquímica
Compostos heterocíclics
Síntesi orgànica
Proves i reactius químics
Heterocyclic compounds
Organic synthesis
Chemical tests and reagents
Issue Date: 27-Aug-2014
Publisher: American Chemical Society
Abstract: The use of the 2-(4-methylphenylsulfonyl)ethenyl (tosvinyl, Tsv) group for the protection of the NH group of a series of imides, azinones (including AZT), inosines, and cyclic sulfonamides has been examined. The Tsv-protected derivatives are obtained in excellent yields by conjugate addition to tosylacetylene (ethynyl p-tolyl sulfone). The stereochemistry of the double bond can be controlled at will: with only 1 mol % of Et3N or with catalytic amounts of NaH, the Z stereoisomers are generated almost exclusively, while the E isomers are obtained using a stoichiometric amount of DMAP. Analogous phenylsulfonylvinyl-protected groups (with the besvinyl or Bsv group instead of Tsv) are obtained stereospecifically by reaction with (Z)- or (E)-bis(phenylsulfonyl)ethene. For lactams and oxazolidinones, this last method is much better. The Tsv and Bsv groups are stable in the presence of non-nucleophilic bases and to acids. They can be removed highly effectively via a conjugate addition-elimination mechanism using pyrrolidine or sodium dodecanethiolate as nucleophiles.
Note: Versió postprint del document publicat a:
It is part of: Journal of Organic Chemistry, 2014, vol. 79, num. 18, p. 8826-8834
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ISSN: 0022-3263
Appears in Collections:Articles publicats en revistes (Química Inorgànica i Orgànica)

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