NMR investigation and theoretical calculations of the effect of solvent on the conformational analysis of 4′,7-di-hydroxy-8-prenylflavan

Abstract

The NMR conformational study of 4′,7-di-hydroxy-8-prenylflavan 1 was carried out in acetone-d6, DMSO-d6 and CDCl3 which enabled the proposition of three conformations, namely 1a, 1b and 1c, differing in the position of the prenyl group. Geometry optimizations performed using AM1 method showed that 1a (ΔHf = -86.2 kcal/mol) is as stable as 1b (ΔHf = -85.1 kcal/mol) and 1c (ΔHf = -85.4 kcal/mol). When the solvent was included, the calculations showed that the solute-solvent interactions could be explained either in the light of the electronic intermolecular delocalization or the electrostatic character between solute and solvent. Theoretical calculations (HF/6-31G*, DFT/BLYP/6-31G*, and DFT/B3LYP/6-31G*) showed that the combination of these types of interactions present in each solute-solvent system, dependent on the chemical properties of the solvent, lead to different spatial arrangements of the prenyl group, which in turn determined the conformation of 1.