Stereochemical and Computational NMR Survey of 1,2,3-Triazoles: in Search of the Original Tauto-Conformers

J Phys Chem A. 2024 May 2;128(17):3231-3240. doi: 10.1021/acs.jpca.3c08217. Epub 2024 Mar 21.

Abstract

The conformational analysis of nine functionalized 1,2,3-triazoles was carried out by the correlation of calculated and experimental high-level nuclear magnetic resonance (NMR) chemical shifts. In solution, the studied triazoles are in exchange dynamic equilibrium caused by their prototropic tautomerism of the NH-proton. The experimentally unresolved NMR signals were assigned for most of the compounds. A more thorough survey was conducted for 4-t-butyl-1,2,3-triazole-5-carbaldehyde oxime. The analysis performed within the framework of the DP4+ formalism completely confirmed the hypothesis of the predominance of the 2H-tautomer. Thus, the methodology for estimating stereochemical structures in the absence of some experimental data allowed the most stable conformations for dynamic systems with different tautomeric ratios to be reliably identified.