Aldehyde-hydrate equilibrium in nucleobase 2-oxoethyl derivatives: An NMR, ESI-MS and theoretical study

• Autores: Nigro, Mariano J.; Brardinelli, Juan I.; Lewkowicz, Elizabeth S.; Iribarren, Adolfo M.; Laurella, Sergio Luis
• Año de publicación: 2017
• Idioma: inglés
• Tipo de recurso: artículo
• Materia: Ciencias Exactas; Química; adenine; thymine; aldehyde; hydrate
• Institución: Universidad Nacional de La Plata

N-2-oxoethyl derivatives of nucleobases are useful starting materials for the preparation of potentially active nucleoside analogues. The ¹HNMR, ¹³CNMR, DEPT and ESI-MS spectra of adenine and thymine N-2-oxoethyl derivatives reveal that the different species in equilibrium exist mainly in two forms: aldehyde and hydrate. The NMR spectra show that the equilibrium is shifted towards the hydrate form in water-DMSO 2:1, giving equilibrium constants of 8.3 and 5.3 for adenine and thymine derivatives, respectively. ESI-MS experiments show the dependence of equilibrium shift on pH: in the case of the thymine derivative, the effect on the equilibrium is more important than in the case of the adenine derivative; this difference is explained considering different protonation sites in both structures. All assumptions are supported by theoretical calculations, which suggest the important role played by solvent in the stabilization of molecular structures and equilibrium shift. All aspects analyzed in this work are very important in order to understand the further reactivity of these nucleobase derivatives.
Facultad de Ciencias Exactas