DFT studies on the favored and rare tautomers of neutral and redox cytosine

• Published in: Structural chemistry Vol. 27; no. 1; pp. 133 - 143
• Main Authors: Raczyńska, Ewa D., Sapuła, Mariusz, Zientara-Rytter, Katarzyna, Kolczyńska, Katarzyna, Stępniewski, Tomasz M., Hallmann, Małgorzata
• Format: Journal Article
• Language: English
• Published: New York Springer US 01.02.2016
• Subjects: Chemistry; Chemistry and Materials Science; Computer Applications in Chemistry; Original Research; Physical Chemistry; Theoretical and Computational Chemistry; Redox forms; Cytosine; Electron delocalization; DFT calculations; Favored and rare tautomers
• ISSN: 1040-0400; 1572-9001
• DOI: 10.1007/s11224-015-0710-9

The complete tautomeric mixture consisting of nine prototropic tautomers has been studied in the gas phase at the DFT(B3LYP)/6-311+G(d,p) level for neutral, oxidized, and reduced cytosine. Rotational isomerism of the exo –OH group and geometrical isomerism of the exo =NH group have also been considered. Tautomeric conversions possible for cytosine have been compared with those for its structural models, 4-amino- and 2-hydroxypyrimidine. Effects of intramolecular interactions between neighboring groups for cytosine are analogous to those observed for model compounds. Although they are not very strong, they are sufficient to influence tautomeric equilibria and relative stabilities of individual tautomers. One-electron oxidation and one-electron reduction change tautomeric preferences. Tautomers that are rare forms for neutral cytosine become favored ones for oxidized and reduced cytosine. Aromaticity is not the main factor that dictates the tautomeric preferences. Stability of functional groups seems to be more important than full electron delocalization.