Selective protonic activation of isomeric glycosylfructoses with pyridinium poly(hydrogen fluoride) and synthesis of spirodioxanyl oligosaccharides.
Selective activation of the ketose unit in the isomeric glycosylfructoses, palatinose, leucrose, maltulose, turanose and lactulose, with pyridinium poly(hydrogen fluoride) resulted in the almost quantitative formation of glycosylated difructose dianhydrides. The reaction preferentially involves a reactive fructofuranosyl oxocarbenium ion and is subject to stereoelectronic control. The relative amounts of isomeric spirodioxanyl oligosaccharides obtained within a series was shown to depend on the reaction conditions, especially on the hydrogen fluoride-pyridine ratio. Using suitable concentrations of hydrogen fluoride in pyridine, the reaction was easily directed to the formation of the kinetic difuranosyl or thermodynamic pyranosyl derivatives. More rigorous conditions resulted in the specific hydrolysis of one glycosidic bond in the tetrasaccharides derived from palatinose, leucrose and turanose, to yield spirodioxanyl trisaccharides.
Defaye
J
J
Laboratoire de Chimie des Glucides, Equipe CNRS, SDI 5509, DRFMC/SESAM, Centre d' Etudes Nucléaires de Grenoble, France.
García Fernández
J M
JM
D000812:Anhydrides / Q000737:chemistry; D002240:Carbohydrate Sequence; D004187:Disaccharides / Q000737:chemistry*; D005632:Fructose / Q000031:analogs & derivatives*; D006858:Hydrofluoric Acid; D007534:Isomaltose / Q000031:analogs & derivatives / Q000737:chemistry; D007792:Lactulose / Q000737:chemistry; D008969:Molecular Sequence Data; D009844:Oligosaccharides / Q000138:chemical synthesis*; D011522:Protons; D011726:Pyridinium Compounds; D013237:Stereoisomerism
D000812:Anhydrides; D004187:Disaccharides; D009844:Oligosaccharides; D011522:Protons; D011726:Pyridinium Compounds; D005632:Fructose; D007792:Lactulose; D007534:Isomaltose; C029454:turanose; D006858:Hydrofluoric Acid; C008189:isomaltulose; C060525:leucrose