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Influence of multiple and cooperative hydrogen bonding on the acidity of polyhydroxylated piperidines: electron density topological analysis

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Abstract

Hydrogen bonds are the presiding concepts for arranging the three-dimensional forms of biological molecules like proteins, carbohydrates, and nucleic acids, and act as guides for proton transfer reactions. Gas-phase acidity and pKa calculations in dimethyl sulfoxide on a line of polyhydroxylated piperidines specify that multiple hydrogen bonds lead to enhance acidities. The gas-phase acidity (GPA) of polyhydroxylated piperidines was investigated by MP2/6-311++G(d,p)//B3LYP/6-311++G(d,p) method. For each structure, varied primary and secondary hydroxyl groups were deprotonated. The natural bond orbital (NBO) and quantum theory of atoms in molecules (QTAIM) analyses have also been used to realize the character of the hydrogen bonding interactions in these compounds. The results show by adding each hydroxyl group, ΔHacid in the gas phase becomes less endothermic and pKa value in the solution phase will decrease. Therefore, intramolecular hydrogen bonds lead to enhance the acid strength. In both the gas and solution phases, the β-nojirimycin-OH2 (β-1-OH2) was found to be the most acidic compound with calculated GPA of 349.4 kcal·mol-1 and the pKa value of 22.0 (8.0 pKa units more acidic than 1-propanol). It was also shown, by applying the polarized continuum model (PCM), there is a superior linear correlation with the GPAs of polyhydroxylated piperidines and their calculated pKa (DMSO) values.

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The datasets used and/or analyzed during the current study are available from the corresponding author on reasonable request.

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Acknowledgments

Support from Tehran Medical Sciences, Islamic Azad University, is gratefully acknowledged.

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  1. Department of Organic Chemistry, Faculty of Pharmaceutical Chemistry, Tehran Medical Sciences, Islamic Azad University, Tehran, Iran

    Marjan Jebeli Javan

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Javan, M.J. Influence of multiple and cooperative hydrogen bonding on the acidity of polyhydroxylated piperidines: electron density topological analysis. Struct Chem 33, 101–111 (2022). https://doi.org/10.1007/s11224-021-01821-y

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