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2014-08-27

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Please use this identifier to cite or link to this item: https://hdl.handle.net/2445/63194

Tosvinyl and besvinyl as protecting groups of imides, azinones, nucleosides, sultams, and lactams. Catalytic conjugate additions to tosylacetylene.

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http://dx.doi.org/10.1021/jo501647w

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.

Subject

Estereoquímica, Compostos heterocíclics, Catàlisi, Síntesi orgànica, Proves i reactius químics

Subject (English)

Stereochemistry, Heterocyclic compounds, Catalysis, Organic synthesis, Chemical tests and reagents

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Articles publicats en revistes (Química Inorgànica i Orgànica)

Citation

PETIT ROIG, Elena, et al. Tosvinyl and besvinyl as protecting groups of imides, azinones, nucleosides, sultams, and lactams. Catalytic conjugate additions to tosylacetylene. Journal of Organic Chemistry. 2014. Vol. 79, num. 18, pags. 8826-8834. ISSN 0022-3263. [consulted: 12 of August of 2026]. Available at: https://hdl.handle.net/2445/63194

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