Determination of the Activation Energy for Pseudorotation of the Furanose Ring in Nucleosides by 13C Nuclear‐Magnetic‐Resonance Relaxation

Abstract

The activation energies for the pseudorotation of the furanose ring in adenosine, guanosine, inosine and xanthosine dissolved in liquid deuteroammonia have been determined by analysis of the longitudinal relaxation rates of the single tertiary carbons between + 40 °C and –60 °C. For the purine ribosides the average activation energy was found to be 4.7 ± 0.5 kcal ± mol−1 (20 ± 2 kJ ± mol−1). For the pyrimidine nucleosides cytidine and uridine the respective activation energy should be higher since it could not be determined by 13C relaxation measurements. This result can be explained by the formation of a hydrogen bond between the 5′‐hydroxymethyl group and the base. In adenosine, guanosine, inosine and xanthosine the relaxation rates of C(5′) are smaller than all others thus excluding the formation of a hydrogen bond between the purine base and the 5′‐hydroxymethyl group of a strength comparable to the one suggested for cytidine and uridine. Copyright © 1975, Wiley Blackwell. All rights reserved