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

• Published in: Chemistry : a European journal Vol. 20; no. 50; pp. 16516 - 16522
• Main Authors: Krylov, Vadim B., Argunov, Dmitry A., Vinnitskiy, Dmitry Z., Verkhnyatskaya, Stella A., Gerbst, Alexey G., Ustyuzhanina, Nadezhda E., Dmitrenok, Andrey S., Huebner, Johannes, Holst, Otto, Siebert, Hans-Christian, Nifantiev, Nikolay E.
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 08.12.2014; WILEY‐VCH Verlag; Wiley; Wiley Subscription Services, Inc
• Subjects: Bacteria; Bacteriology; Carbohydrate Sequence; Carbohydrates; Chemistry; Chemistry, Multidisciplinary; Derivatives; Enterococcus faecalis - chemistry; furanoside; Glycosides - chemical synthesis; Glycosides - chemistry; Glycosylation; Klebsiella; Klebsiella pneumoniae - chemistry; Models, Molecular; Molecular Sequence Data; Oligosaccharides; Oligosaccharides - chemical synthesis; Oligosaccharides - chemistry; Physical Sciences; rearrangement; Science & Technology; Seaweed - chemistry; Seaweeds; sulfation; Synthesis (chemistry); Transformations; carbohydrates; GLYCOSIDES; furanoside; NMR-SPECTROSCOPY; GALACTOFURANOSE; glycosylation; DONORS; BIOSYNTHESIS; sulfation; rearrangement; KLEBSIELLA-PNEUMONIAE; POLYSACCHARIDE; FUCOIDANS; ANTIGEN
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.201405083

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. Breaking new ground: The new reaction of pyranoside‐into‐furanoside rearrangement was developed and successfully applied for the synthesis of different types of oligosaccharide models for biological investigations (see scheme).