A kinetic estimate of the free aldehyde content of aldoses.
The relative free aldehyde content of eight hexoses and four pentoses has been estimated within about 10% from the rate constants for their reaction with urazole (1,2,4-triazole-3,5-dione). These values of the percent free aldehyde are in agreement with those estimated from CD measurements, but are more accurate. The relative free aldehyde contents for the aldoses were then correlated to various literature NMR measurements to obtain the absolute values. This procedure was also done for three deoxyaldoses, which react much more rapidly than can be accounted for by the free aldehyde content. This difference in reactivity between aldoses and deoxyaldoses is due to the inductive effect of the H versus the OH on C-2'. This may help explain why deoxyribonucleosides hydrolyze much more rapidly than ribonucleosides.
Dworkin
J P
JP
Department of Chemistry and Biochemistry, University of California, San Diego, La Jolla 92093-0506, USA.
Miller
S L
SL
D000447:Aldehydes / Q000032:analysis*; D002942:Circular Dichroism; D003837:Deoxy Sugars / Q000737:chemistry; D006601:Hexoses / Q000737:chemistry*; D007700:Kinetics; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D010429:Pentoses / Q000737:chemistry*; D013329:Structure-Activity Relationship; D014230:Triazoles / Q000737:chemistry
D000447:Aldehydes; D003837:Deoxy Sugars; D006601:Hexoses; D010429:Pentoses; D014230:Triazoles; C421465:urazole