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Pyranoside‐into‐Furanoside Rearrangement: New Reaction in Carbohydrate Chemistry and Its Application in Oligosaccharide Synthesis
Author(s) -
Krylov Vadim B.,
Argunov Dmitry A.,
Vinnitskiy Dmitry Z.,
Verkhnyatskaya Stella A.,
Gerbst Alexey G.,
Ustyuzhanidezhda E.,
Dmitrenok Andrey S.,
Huebner Johannes,
Holst Otto,
Siebert HansChristian,
Nifantiev Nikolay E.
Publication year - 2014
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201405083
Subject(s) - chemistry , disaccharide , ring (chemistry) , carbohydrate , stereochemistry , pyran , monosaccharide , polysaccharide , oligosaccharide , klebsiella pneumoniae , carbohydrate chemistry , organic chemistry , biochemistry , escherichia coli , gene
Great 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 ‐Gal p ‐(1→3)‐β‐ D ‐ Gal f ‐OPr, 3‐ O ‐ s ‐lactyl‐β‐ D ‐ Gal f ‐(1→3)‐β‐ D ‐Glc p ‐OPr, and α‐ L ‐ Fuc f ‐(1→4)‐β‐ D ‐Glc p A‐OPr related to polysaccharides from the bacteria Klebsiella pneumoniae and Enterococcus faecalis and the brown seaweed Chordaria flagelliformis .