Acyclic Forms of [1-13C]Aldohexoses in Aqueous Solution: Quantitation by 13C NMR and Deuterium Isotope Effects on Tautomeric Equilibria

Citations Over TimeTop 15% of 2001 papers

Abstract

High-resolution (13)C NMR spectra (150 MHz) have been obtained on the complete series of D-aldohexoses (D-allose 1, D-altrose 2, D-galactose 3, D-glucose 4, D-gulose 5, D-idose 6, D-mannose 7, D-talose 8) selectively labeled with (13)C at C1 in order to detect and quantify the percentages of acyclic forms, and to measure and/or confirm percentages of furanoses and pyranoses, in aqueous solution. Aldehyde and hydrate signals were detected for all aldohexoses, and percentages of these forms at 30 degrees C ranged from 0.006 to 0.7% (hydrate) and 0.0032 to 0.09% (aldehyde). Aldehyde percentages are largest for the altro, ido, and talo configurations, ranging from 0.01 to 0.09%; the ido configuration yielded the most hydrate (0.74%). Hydrate/aldehyde ratios vary with aldohexose configuration, ranging from 1.5 to 13, with gluco exhibiting the smallest ratio and gulo the largest. (2)H Equilibrium isotope effects (EIEs) on aldohexose anomerization were measured in D-galactose 3 and D-talose 8 selectively (13)C- and (2)H-labeled at C1 and H1. The (2)H isotope effect on (13)C chemical shift, and broadband (1)H- and (2)H-decoupling, were exploited to permit simultaneous observation and quantitation of the protonated and deuterated molecules in NMR samples containing equimolar mixtures of D-[1-(13)C]aldose and D-[1-(13)C; 1-(2)H]aldose. Small (2)H EIEs were observed for 8, but were undetectable for 3. These results suggest that configuration at C2 influences the magnitude of the (2)H isotope effect at H1 and/or that the observed effect cannot be reliably interpreted due to complications arising from the involvement of acyclic aldehyde forms as intermediates in the interconversion of cyclic forms. The observed (2)H isotope effects on aldohexose tautomeric equilibria provide new insights into the important question of whether (2)H substitutions can alter aldofuranose ring conformation, and lead to the identification of an optimal (2)H- and (13)C-substituted 2-deoxyribofuranose isotopomer on which to investigate this potential effect.

Related Papers

• → Nitrogen and deuterium kinetic isotope effects on the Menshutkin reaction(1996)17 cited
• → Large primary kinetic isotope effects in the abstraction of hydrogen from organic compounds by a fluorinated radical in waterElectronic supplementary information (ESI) available: Tables of kinetic data and plots of kinetic data. See http://www.rsc.org/suppdata/ob/b4/b405075d/(2004)6 cited
• → Secondary Deuterium Isotope Effects on Reactions Proceeding Through Carbocations(1983)24 cited
• → Calculations of intrinsic isotope effects and the detection of tunneling in enzyme-catalyzed reactions(1990)10 cited
• Kinetic Deuterium Isotope Effects on the Reactions of 2-(4-Methoxyphenyl)Oxirane in Water Solutions(2006)