title: [13C,15N]2-Acetamido-2-deoxy-D-aldohexoses and their methyl glycosides: synthesis and NMR investigations of J-couplings involving 1H, 13C, and 15N.
abstract: [reaction: see text] A series of 2-amino-2-deoxy-D-[1-13C]aldohexoses and their methyl glycosides was prepared with use of a simplified cyanohydrin reduction route. Four d-aldopentosylamines (arabino, lyxo, ribo, xylo) were prepared from the corresponding D-aldopentoses by reaction with NH3(g) in MeOH solvent, isolated in solid form, and characterized by 13C and 1H NMR. Hydrolysis of beta-D-xylopyranosylamine was studied using 13C-labeled substrates to establish optimal solution conditions for cyanohydrin formation. Major hydrolytic intermediates were observed and identified by time-lapse 1D and 2D NMR analyses of reaction mixtures. The aldopentosylamines were subsequently employed in cyanohydrin reduction reactions with K13CN to yield C2-epimeric [1-13C]2-aminosugars, which were separated by chromatography on ion-exchange columns. N-Acetylation and methyl glycosidation followed by chromatography gave pure 2-acetamido-2-deoxy-D-[1-13C]aldohexopyranosides. J(CH) and J(CC) spin-spin coupling constants involving the labeled anomeric carbon were measured and compared to those observed previously in methyl D-[1-13C]aldohexopyranosides. In parallel studies, theoretical J-couplings were calculated in model N-acetylated aldopyranosides using density functional theory (DFT) to predict the effect of OH vs NHCOCH(3) substitution at C2 on J(CH) and J(CC) values in aldopyranosyl rings. The synthetic method was also modified to accommodate (15)N- and (13)C-labeling within the N-acetyl side-chain, and some J-couplings involving 1H, 13C, and 15N atoms in 2-[1,2-13C2;15N]acetamido-2-deoxy-D-[1-13C]glucose were measured and interpreted.
authors.affiliation: Department of Chemistry and Biochemistry and the Radiation Laboratory, University of Notre Dame, Notre Dame, Indiana 46556-5670, USA.
authors.forename: Yuping
authors.initials: Y
authors.lastname: Zhu
authors.forename: Qingfeng
authors.initials: Q
authors.lastname: Pan
authors.forename: Christophe
authors.initials: C
authors.lastname: Thibaudeau
authors.forename: Shikai
authors.initials: S
authors.lastname: Zhao
authors.forename: Ian
authors.initials: I
authors.lastname: Carmichael
authors.forename: Anthony S
authors.initials: AS
authors.lastname: Serianni
mesh_terms: D002236:Carbohydrate Conformation; D002240:Carbohydrate Sequence; D002247:Carbon Isotopes; D002851:Chromatography, High Pressure Liquid; D006027:Glycosides / Q000138:chemical synthesis* / Q000737:chemistry; D006601:Hexoses / Q000138:chemical synthesis* / Q000737:chemistry; D006859:Hydrogen; D009682:Magnetic Resonance Spectroscopy / Q000379:methods; D013058:Mass Spectrometry; D008969:Molecular Sequence Data; D009584:Nitrogen; D009844:Oligosaccharides / Q000138:chemical synthesis
chemical_list: D002247:Carbon Isotopes; D006027:Glycosides; D006601:Hexoses; D009844:Oligosaccharides; D006859:Hydrogen; D009584:Nitrogen