478529-42-9Relevant articles and documents
[13C,15N]2-acetamido-2-deoxy-D-aldohexoses and their methyl glycosides: Synthesis and NMR investigations of J-couplings involving1H, 13C, and15N
Zhu, Yuping,Pan, Qingfeng,Thibaudeau, Christophe,Zhao, Shikai,Carmichael, Ian,Serianni, Anthony S.
, p. 466 - 479 (2007/10/03)
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 glycosklation followed by chromatography gave pure 2-acetamido-2-deoxy-D-[1-13C]aldohexopyranosicles, JCH and JCC 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 NHCOCH3 substitution at C2 on JCH and JCC values in aldopyranosyl rings. The synthetic method was also modified to accommodate 15N- and 13C-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.
