Conformational preferences and intramolecular hydrogen bonding patterns of tetraflavaspidic acid BBBB – a tetrameric acylphloroglucinol

Abstract

Abstract Tetraflavaspidic acid BBBB is a tetrameric acylphloroglucinol of natural origin isolated from Dryopteris aitoniana. Its molecule consists of four acylphloroglucinol units linked by methylene bridges and having the same R = propyl in their R−C=O groups. In one of the terminal monomers, one of the OHs ortho to R−C=O is replaced by a keto O. The paper reports the results of a conformational study performed at the HF/6-31G(d,p) and DFT/B3LYP/6-31+G(d,p) levels; two options are utilised for the latter, without and with the inclusion of the Grimme’s dispersion correction. Given the importance of intramolecular hydrogen bonds (IHBs) for the stabilisation of acylphloroglucinol conformers, only conformers containing the maximum IHBs’ number were calculated. The IHBs comprise an IHB between the sp2 O of R−C=O and a neighbouring OH in each monomeric unit and two inter-monomer IHBs between each pair of units. The single C−C bonds of the methylene bridges enable a variety of mutual orientations of the monomeric units, giving rise to a variety of conformations and IHB patterns. The results indicate greater stability for conformers in which individual monomers take lower energy conformations, and significant influence of the dispersion correction on the estimation of the energetics and of other molecular properties. The inclusion of the dispersion correction also strongly limits the number of low energy conformers. The influence of dispersion effects is consistent with the presence of four aromatic rings.