Pyranoside‐into‐Furanoside Rearrangement: New Reaction in Carbohydrate Chemistry and Its Application in Oligosaccharide Synthesis

Publisher： John Wiley & Sons Inc

E-ISSN： 1521-3765|20|50|16516-16522

ISSN： 0947-6539

Source： CHEMISTRY - A EUROPEAN JOURNAL, Vol.20, Iss.50, 2014-12, pp. : 16516-16522

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Abstract

AbstractGreat interest in natural furanoside‐containing compounds has challenged the development of preparative methods for their synthesis. Herein a novel reaction in carbohydrate chemistry, namely a pyranoside‐into‐furanoside (PIF) rearrangement permitting the transformation of selectively O‐substituted pyranosides into the corresponding furanosides is reported. The discovered process includes acid‐promoted sulfation accompanied by rearrangement of the pyranoside ring into a furanoside ring followed by solvolytic O‐desulfation. This process, which has no analogy in organic chemistry, was shown to be a very useful tool for the synthesis of furanoside‐containing complex oligosaccharides, which was demonstrated by synthesizing disaccharide derivatives α‐D‐Galp‐(1→3)‐β‐D‐Galf‐OPr, 3‐O‐s‐lactyl‐β‐D‐Galf‐(1→3)‐β‐D‐Glcp‐OPr, and α‐L‐Fucf‐(1→4)‐β‐D‐GlcpA‐OPr related to polysaccharides from the bacteria Klebsiella pneumoniae and Enterococcus faecalis and the brown seaweed Chordaria flagelliformis.