A theoretical insight into the formation mechanisms of C/N-ribonucleosides with pyrimidine and ribose.
Phys Chem Chem Phys
; 19(16): 10413-10426, 2017 Apr 19.
Article
em En
| MEDLINE
| ID: mdl-28379245
ABSTRACT
The detailed formation mechanisms of C-ribonucleoside and N-ribonucleoside via the reaction of 2,4,6-triaminopyrimidine (TAP) with (d)-ribose in aqueous solution were explored using density functional theory (DFT). The calculations indicate that five isomers (α,ß-furanose, α,ß-pyranose and open-chain aldehyde) of (d)-ribose can exist in equilibrium in aqueous solution. In contrast to cyclic isomers, an open-chain aldehyde is most feasible to react with TAP. In general, the formation pathways of C-nucleoside and N-nucleoside proceed in three steps including nucleophilic addition, dehydration and cyclization. The calculated apparent activation energies are 28.8 kcal mol-1 and 29.2 kcal mol-1, respectively. It suggests that both C- and N-nucleoside can be formed in aqueous solution, which is in good agreement with the experimental results. The water molecule plays an important "H-bridge" role by the hydrogen atom relay. Finally, a model structure of nucleobase, which will be beneficial for the C-C glycosidic bond formation, is proposed.
Texto completo:
1
Coleções:
01-internacional
Base de dados:
MEDLINE
Assunto principal:
Pirimidinas
/
Ribonucleosídeos
/
Ribose
/
Modelos Moleculares
Idioma:
En
Ano de publicação:
2017
Tipo de documento:
Article