Tautomeric preference in lumazines, deazalumazines, isoalloxazines and pyrimidines and its effect on the reactivity of alkyl groups

Svetlana A Kondrashova; Fedor M Polyancev; Shamil K Latypov

doi:10.1016/j.bioorg.2021.104725

Tautomeric preference in lumazines, deazalumazines, isoalloxazines and pyrimidines and its effect on the reactivity of alkyl groups

Bioorg Chem. 2021 Apr:109:104725. doi: 10.1016/j.bioorg.2021.104725. Epub 2021 Feb 11.

Authors

Svetlana A Kondrashova¹, Fedor M Polyancev¹, Shamil K Latypov²

Affiliations

¹ Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of RAS, Russia.
² Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of RAS, Russia. Electronic address: lsk@iopc.ru.

PMID: 33611139
DOI: 10.1016/j.bioorg.2021.104725

Abstract

In lumazines, deazalumazines and pyrimidines, there are extremely low-energy "rare" tautomers (<2.3 kcal/mol), this fact perfectly explains the observed mobility of usually "non-labile" protons of methyl groups in such systems. In general, the dependence of tautomeric preference on structure correlates well with experimental findings. Thus, the activity of alkyl groups during biological transformations may be due to the presence of the corresponding thermodynamically stable tautomers.

Keywords: DFT study; Hydrogen-deuterium exchange; N-heterocycles; Tautomerism.

MeSH terms

Density Functional Theory
Flavins / chemistry*
Molecular Structure
Pteridines / chemistry*
Pyrimidines / chemistry*
Thermodynamics

Substances

Flavins
Pteridines
Pyrimidines
lumazine
isoalloxazine