Title:
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Tosvinyl and besvinyl as protecting groups of imides, azinones, nucleosides, sultams, and lactams. Catalytic conjugate additions to tosylacetylene.
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Author:
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Petit, Elena; Bosch Hereu, Lluís; Font, Joan; Mola, Laura; Costa i Arnau, Anna M.; Vilarrasa i Llorens, Jaume
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Other authors:
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Universitat de Barcelona |
Abstract:
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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. |
Subject(s):
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-Estereoquímica -Compostos heterocíclics -Catàlisi -Síntesi orgànica -Proves i reactius químics -Stereochemistry -Heterocyclic compounds -Catalysis -Organic synthesis -Chemical tests and reagents |
Rights:
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(c) American Chemical Society , 2014
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Document type:
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Article Article - Accepted version |
Published by:
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American Chemical Society
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