α- and β-Glycosyl sulfonium ions: Generation and reactivity

Toshiki Nokami, Akito Shibuya, Shino Manabe, Yukishige Ito, Jun Ichi Yoshida

Research output: Contribution to journalArticlepeer-review

54 Citations (Scopus)

Abstract

A study was conducted to observe the generation and reactivity of α- and β-glycosyl sulfonium ions. Preparation of a glycosyl triflate of 2-deoxy-2-amino sugar was done from a thioglycoside using glycosyl triflate pool method. The triflate oxygen was bound covalently to the anomeric carbon due to chemical shift of the anomeric carbon. It was found that α- and β-glycosyl sulfonium ions were produced from an electrochemically generated glycosyl triflate. The NMR spectroscopy and mass spectrometry were used to characterized these ions. The reaction with MeOH showed that the α-glycosyl sulfonium ion had more reactivity compared to β-glycosyl sulfonium ion. The stereochemical results revealed that the reaction failed to proceed by a simple SN2 mechanism and proceeded through glycosyl cation intermediate. The study opened new opportunities for mechanistic studies on glycosylation reactions.

Original languageEnglish
Pages (from-to)2252-2255
Number of pages4
JournalChemistry - A European Journal
Volume15
Issue number10
DOIs
Publication statusPublished - 2009 Feb 23
Externally publishedYes

Keywords

  • Carbohydrates
  • Glycosylation
  • NMR spectroscopy
  • Oxidation
  • Stereochemistry

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

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