NMR studies in the syn-anti dynamic equilibrium in purine nucleosides and nucleotides

The syn in equilibrium anti equilibrium conformation about the glycosidic bond of purine nucleosides and 5'-nucleotides in different solvent systems has been investigated by means of 1H NMR spectroscopy. Quantitative values for the conformer populations were improved, relative to previous results, by a detailed study of, and a resultant derived correction for, the influence of the sugar exocyclic group conformation on the chemical shifts of the sugar ring protons. This was achieved with the aid of nucleosides and nucleotides fixed in the conformations gauche-trans [derivatives of 8,5'-(R)-cyclo] and trans-gauche [derivatives of 8,5'-(S)-cyclo]. The results of 13C NMR confirmed those obtained by 1H NMR. The measured values of the vicinal coupling constants between H-1' and the C-8 and C-4 carbons were employed to evaluate approximately the glycosidic angles chi of the nucleosides in the conformations syn and anti. A critical examination is made of the applicability of relaxation methods, involving analysis of spin-lattice relaxation time of protons (T1) and the Overhauser effect, to determine the conformation of the base about the glycosidic bond; interpretations are provided for the lack of agreement between these methods and those based on chemical shifts in the present study. The foregoing resuls are also applied to an examination of the effect of the conformation of the base about the glycosidic bond on the enzymatic reactions catalyzed by 5'-nucleotidase and adenosine deaminase.