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6566700 
Journal Article 
Pyranoside-into-furanoside rearrangement: new reaction in carbohydrate chemistry and its application in oligosaccharide synthesis 
Krylov, VB; Argunov, DA; Vinnitskiy, DZ; Verkhnyatskaya, SA; Gerbst, AG; Ustyuzhanina, NE; Dmitrenok, AS; Huebner, J; Holst, O; Siebert, HC; Nifantiev, NE 
2014 
Yes 
Chemistry: A European Journal
ISSN: 0947-6539
EISSN: 1521-3765 
20 
50 
16516-16522 
English 
25319316 
WOS:000346055800016 
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.