Pyranoside‐into‐Furanoside Rearrangement: New Reaction in Carbohydrate Chemistry and Its Application in Oligosaccharide Synthesis |
| |
Authors: | Dr. Vadim B. Krylov Dmitry A. Argunov Dmitry Z. Vinnitskiy Stella A. Verkhnyatskaya Dr. Alexey G. Gerbst Dr. Nadezhda E. Ustyuzhanina Dr. Andrey S. Dmitrenok Prof. Dr. Johannes Huebner Prof. Dr. Otto Holst Prof. Dr. Hans‐Christian Siebert Prof. Dr. Nikolay E. Nifantiev |
| |
Affiliation: | 1. Laboratory of Glycoconjugate Chemistry, N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky prospect 47, 119991 Moscow (Russian Federation);2. Division of Pediatric Infectious Diseases, Hauner Children's Hospital, Ludwigs‐Maximilian University, Munich (Germany);3. Research Center Borstel, Leibniz‐Center for Medicine and Biosciences, Borstel (Germany);4. RI‐B‐NT ‐ Research Institute of Bioinformatics and Nanotechnology, 24118 Kiel (Germany) |
| |
Abstract: | 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 ‐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. |
| |
Keywords: | carbohydrates furanoside glycosylation rearrangement sulfation |
|
|