Synlett 2016; 27(11): 1659-1664
DOI: 10.1055/s-0035-1561595
letter
© Georg Thieme Verlag Stuttgart · New York

The Pyranoside-into-Furanoside Rearrangement of Alkyl Glycosides: Scope and Limitations

Vadim B. Krylov
Laboratory of Glycoconjugate Chemistry, N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky Prospect 47, 119991 Moscow, Russian Federation   eMail: nen@ioc.ac.ru
,
Dmitry A. Argunov
Laboratory of Glycoconjugate Chemistry, N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky Prospect 47, 119991 Moscow, Russian Federation   eMail: nen@ioc.ac.ru
,
Dmitry Z. Vinnitskiy
Laboratory of Glycoconjugate Chemistry, N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky Prospect 47, 119991 Moscow, Russian Federation   eMail: nen@ioc.ac.ru
,
Alexey G. Gerbst
Laboratory of Glycoconjugate Chemistry, N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky Prospect 47, 119991 Moscow, Russian Federation   eMail: nen@ioc.ac.ru
,
Nadezhda E. Ustyuzhanina
Laboratory of Glycoconjugate Chemistry, N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky Prospect 47, 119991 Moscow, Russian Federation   eMail: nen@ioc.ac.ru
,
Andrey S. Dmitrenok
Laboratory of Glycoconjugate Chemistry, N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky Prospect 47, 119991 Moscow, Russian Federation   eMail: nen@ioc.ac.ru
,
Nikolay E. Nifantiev*
Laboratory of Glycoconjugate Chemistry, N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky Prospect 47, 119991 Moscow, Russian Federation   eMail: nen@ioc.ac.ru
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Publikationsverlauf

Received: 25. November 2015

Accepted after revision: 03. März 2016

Publikationsdatum:
06. April 2016 (online)


Abstract

The pyranoside-into-furanoside (PIF) rearrangement was recently reported as a useful tool for the synthesis of furanoside-containing complex oligosaccharides. Until now, this transformation has only been described for some protected allyl-β-d-galactosides and one l-fucoside. In this communication its applicability is expanded. The formation of furanosides was observed under acid-promoted sulfation for a series of galactosides with varying alkyl substituents at the anomeric position as well as for several fucosides and glucosides. Meanwhile, furanoside formation was not detected in the case of mannopyranosides. The different reactivity of substrates was explained by values of activation barriers of endocyclic C1–O5 bond cleavage calculated by ab initio RHF methods. The reported results clarify the scope and limitations of the PIF rearrangement, which is important for its application in the synthesis of carbohydrate structures of practical meaning.

Supporting Information

 
  • References and Notes

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