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, Sándor Antus, Anikõ Borbás

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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 - szept. 1 2013

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ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry

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