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http://hdl.handle.net/2445/63194
Title: | Tosvinyl and besvinyl as protecting groups of imides, azinones, nucleosides, sultams, and lactams. Catalytic conjugate additions to tosylacetylene. |
Author: | Petit Roig, Elena Bosch Hereu, Lluís Font, Joan Mola Solà, Laura Costa i Arnau, Anna M. Vilarrasa i Llorens, Jaume |
Keywords: | Estereoquímica Compostos heterocíclics Catàlisi Síntesi orgànica Proves i reactius químics Stereochemistry Heterocyclic compounds Catalysis 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: http://dx.doi.org/10.1021/jo501647w |
It is part of: | Journal of Organic Chemistry, 2014, vol. 79, num. 18, p. 8826-8834 |
URI: | http://hdl.handle.net/2445/63194 |
Related resource: | http://dx.doi.org/10.1021/jo501647w |
ISSN: | 0022-3263 |
Appears in Collections: | Articles publicats en revistes (Química Inorgànica i Orgànica) |
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