Synthesis of 6-sulfonatomethyl thioglycosides by nucleophilic substitution: Methods to prevent 1→6 anomeric group migration of thioglycoside 6-o-triflates

Mihály Herczeg, Erika Mezo, Dániel Eszenyi, Lászlõ Lázár, Magdolna Csávás, Ilona Bereczki, S. Antus, A. Borbás

Research output: Contribution to journalArticle

6 Citations (Scopus)

Abstract

Introduction of a sulfonatomethyl moiety into the primary position of thioglycosides by nucleophilic displacement of the corresponding 6-O-triflate is described. The 1→6 migration of the anomeric group, which inevitably occurs through a bicyclic sulfonium ion intermediate, from conformationally flexible β-thioglycosides was prevented by using an α-thioglycoside or conformationally locked β-thioglycoside as the starting material. The thioglycoside 6-sulfonic acids showed excellent α-selectivity during synthesis of uronic acid containing heparinoid trisaccharides. Two routes to prepare C6-sulfonatomethyl thioglucosides by displacement of a 6-O-triflate moiety are reported. The undesired participation of the β-thio aglycon is prevented by changing the anomeric configuration or by locking the pyranose ring. The 6-sulfonatomethyl donors show excellent α-selectivities but significantly different reactivities during the synthesis of heparinoid trisaccharides.

Original languageEnglish
Pages (from-to)5570-5573
Number of pages4
JournalEuropean Journal of Organic Chemistry
Issue number25
DOIs
Publication statusPublished - Sep 2013

Fingerprint

Thioglycosides
Substitution reactions
selectivity
substitutes
Heparinoids
sulfonic acid
synthesis
Trisaccharides
locking
reactivity
routes
Thioglucosides
acids
rings
Uronic Acids
configurations
Sulfonic Acids
ions
Ions

Keywords

  • Carbohydrates
  • Glycosylation
  • Nucleophilic substitution
  • Sulfonic acids
  • Sulfur

ASJC Scopus subject areas

  • Organic Chemistry
  • Physical and Theoretical Chemistry

Cite this

Synthesis of 6-sulfonatomethyl thioglycosides by nucleophilic substitution : Methods to prevent 1→6 anomeric group migration of thioglycoside 6-o-triflates. / Herczeg, Mihály; Mezo, Erika; Eszenyi, Dániel; Lázár, Lászlõ; Csávás, Magdolna; Bereczki, Ilona; Antus, S.; Borbás, A.

In: European Journal of Organic Chemistry, No. 25, 09.2013, p. 5570-5573.

Research output: Contribution to journalArticle

Herczeg, Mihály ; Mezo, Erika ; Eszenyi, Dániel ; Lázár, Lászlõ ; Csávás, Magdolna ; Bereczki, Ilona ; Antus, S. ; Borbás, A. / Synthesis of 6-sulfonatomethyl thioglycosides by nucleophilic substitution : Methods to prevent 1→6 anomeric group migration of thioglycoside 6-o-triflates. In: European Journal of Organic Chemistry. 2013 ; No. 25. pp. 5570-5573.
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