Abstract
Parameters of restricted internal rotation about the C–C bond of the O–C–C–N fragment in the neutral and protonated forms of noradrenaline in D2O, CD3OD, and DMSO-d6 were estimated by quantum molecular dynamics and NMR methods. The one-dimensional internal rotation potentials were calculated in the MP2/aug-cc-pVTZ approximation. The multiplet structure of the 1H NMR spectra of neutral and protonated noradrenaline in the given solvent series was resolved, and signals of diastereotopic methylene protons pro-S and pro-R were assigned. The conformational dependences of the proton coupling constants were calculated at the FPT-DFT 6-311++G(2df,2p) level of theory. The relative contributions of different rotamers were evaluated by solving a series of inverse vibrational problems in terms of the large-amplitude vibration model to achieve the best agreement between the calculated and experimental coupling constants. The neutral form of noradrenaline was shown to prefer conformation g+, while conformer g− was found to be the minor one. Protonation of noradrenaline molecule essentially stabilizes conformer g−. In all cases, the contribution of conformer t with transoid orientation of the oxygen and nitrogen atoms did not exceed 1%. The obtained data can be useful for the construction of a quantitative model for noradrenaline binding to receptors at the molecular level.
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For communication II, see [1].
Russian Text © The Author(s), 2019, published in Zhurnal Organicheskoi Khimii, 2019, Vol. 55, No. 3, pp. 411–419.
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Ganina, T.A., Chertkov, V.A. Dynamic Structure of Organic Compounds in Solution According to NMR Data and Quantum Chemical Calculations: III. Noradrenaline. Russ J Org Chem 55, 354–361 (2019). https://doi.org/10.1134/S107042801903014X
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DOI: https://doi.org/10.1134/S107042801903014X