[13C,15N]2-Acetamido-2-deoxy-d-aldohexoses and Their Methyl Glycosides: Synthesis and NMR Investigations of J-Couplings Involving 1H, 13C, and 15N

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 β-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. JCH and JCC spin−spin coupling constants involving the labeled anomeric ca...