Synthesis of dispirodioxanyl pseudo-oligosaccharides by selective protonic activation of isomeric glycosylfructoses in anhydrous hydrogen fluoride.
Dispirodioxanyl pseudotetrasaccharides 6-O-alpha-D-glucopyranosyl-alpha-D-fructofuranose 6-O-alpha-D-glucopyranosyl-beta-D-fructofuranose 1,2':2,1'-dianhydride, 5-O-alpha-D-glucopyranosyl-alpha-D-fructopyranose 5-O-alpha-D-glucopyranosyl-beta-D-fructopyranose 1,2':2,1'-dianhydride, 4-O-alpha-D-glucopyranosyl-alpha-D-fructofuranose 4-O-alpha-D-glucopyranosyl-beta-D-fructopyranose 1,2':2,1'-dianhydride, 4-O-beta-D-galactopyranosyl-alpha-D-fructofuranose 4-O-beta-D-galactopyranosyl-beta-D-fructopyranose 1,2':2,1'-dianhydride, and 3-O-alpha-D-glucopyranosyl-alpha-D-fructofuranose 3-O-alpha-D-glucopyranosyl-beta-D-fructofuranose 1,2':2,1'-dianhydride were respectively obtained, on a preparative scale, by dissolution of the isomeric glycosylfructoses palatinose, leucrose, maltulose, lactulose, and turanose in anhydrous hydrogen fluoride. The reaction, involving selective protonation at the free anomeric position of the fructose unit, was extended to the preparation of the pseudotrisaccharides 6-O-alpha-D-glucopyranosyl-alpha-D-fructofuranose beta-D-fructopyranose 1,2':2',1-dianhydride from palatinose and fructose, and to its 3-O-, 4-O-, and 4'-O-glucosyl analogues using turanose and maltulose as the disaccharide precursor. The cross-reactions of palatinose with maltulose and with leucrose resulted in the preparation of 6-O-alpha-D-glucopyranosyl-alpha-D-fructofuranose 4-O-alpha-D-glucopyranosyl-beta-D-fructopyranose 1,2':2,1'-dianhydride and 6-O-alpha-D-glucopyranosyl-alpha-D-fructofuranose 5-O-alpha-D-glucopyranosyl-beta-D-fructopyranose 1,2':2,1'-dianhydride, respectively.
Defaye
J
J
Département de Recherche Fondamentale, Matière Condensée/SESAM, Centre d'Etudes de Grenoble, France.
García Fernández
J M
JM
D000812:Anhydrides / Q000737:chemistry; D002240:Carbohydrate Sequence; D004146:Dioxanes / Q000737:chemistry; D004187:Disaccharides / Q000737:chemistry*; D006858:Hydrofluoric Acid / Q000737:chemistry; D007534:Isomaltose / Q000031:analogs & derivatives / Q000737:chemistry; D007536:Isomerism; D007792:Lactulose / Q000737:chemistry; D008969:Molecular Sequence Data; D009844:Oligosaccharides / Q000737:chemistry*; D011522:Protons
D000812:Anhydrides; D004146:Dioxanes; D004187:Disaccharides; D009844:Oligosaccharides; D011522:Protons; D007792:Lactulose; D007534:Isomaltose; C029454:turanose; D006858:Hydrofluoric Acid; C008189:isomaltulose; C060525:leucrose