Protonic reactivity of sucrose in anhydrous hydrogen fluoride.
Sucrose reacts quantitatively, when dissolved at high concentration in anhydrous hydrogen fluoride, to afford a complex mixture of difructose dianhydrides and their glucosylated derivatives. Oligo- and small poly-saccharides up to dp 14 were detected by FABMS. Oligosaccharides up to dp 4, representing approximately 50% of the total mixture, have been isolated and characterized by mass spectrometry, 13C NMR spectroscopy, and comparison with reference oligosaccharides previously obtained by unambiguous synthesis. alpha-D-Fructofuranose beta-D-fructopyranose 1,2':2,1'-dianhydride is the main spirodioxanyl pseudodisaccharide entity found in the mixture, either free or glucosylated at C-6 and to a lesser extent at C-3, C-4, C-4', C-6, and C-5' C-6. Minor spirodioxanyl pseudodisaccharide components are di-beta-D-fructopyranose 1,2':2,1'-dianhydride, which has also been found glucosylated at C-5, alpha-D-fructopyranose beta-D-fructopyranose 1,2':2,1'-dianhydride, beta-D-fructofuranose beta-D-fructopyranose 1,2':2,3'-dianhydride, and the 6,6'-diglucosylated alpha-D-fructofuranose beta-D-fructofuranose 1,2':2,1'-dianhydride. A 13C NMR examination of the higher mass oligomeric fraction suggests that it may involve 6-O-isomaltooligoglycosyl alpha-D-fructofuranose beta-D-fructopyranose 1,2':2,1'-dianhydrides as the main structural components. The reaction of sucrose in anhydrous HF is believed to proceed through initial selective protonic activation of the tertiary anomeric carbon atom of the fructose moiety, resulting in the quantitative formation of difructose dianhydrides, which subsequently suffer electrophilic substitution by glucopyranosyl oxocarbenium ions generated in a second step by action of the HF.
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; D002247:Carbon Isotopes; D005632:Fructose / Q000737:chemistry; D006858:Hydrofluoric Acid / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D008969:Molecular Sequence Data; D009844:Oligosaccharides / Q000737:chemistry; D011522:Protons; D013395:Sucrose / Q000737:chemistry*; D014312:Trisaccharides / Q000737:chemistry
D000812:Anhydrides; D002247:Carbon Isotopes; D009844:Oligosaccharides; D011522:Protons; D014312:Trisaccharides; D005632:Fructose; D013395:Sucrose; D006858:Hydrofluoric Acid