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High Resolution NMR Spectra and Dynamic Structure of Vinylcyclopropaneтезисы доклада
- Авторы: Stanishevskiy V.V., Cheshkov D.A., Shestakova A.K., Ganina T.A., Chertkov V.A.
- Сборник: 15 International school-conference "Magnetic resonance and its applications" Abstract book
- Тезисы
- Год издания: 2018
- Место издания: BBM Санкт-Петербург Санкт-Петербург
- Первая страница: 182
- Последняя страница: 182
- Аннотация: The present work was aimed at quantifying the dynamic structure of noradrenalin and its protonated form according to NMR data and quantum mechanical calculations. Conformational dynamics in noradrenalin proceeds due to extremely fast processes of internal rotation around simple bonds C1-C2 and C4’-C1. The dynamic structure of noradrenalin and its protonated form in D2O, CD3OD and DMSO D6 solutions have been studied with the goal of obtaining accurate information to simulate molecular mechanisms of their action in living systems. The potential energy surface for internal rotation about the single С1 С2 bond has been constructed in terms of the Møller–Plesset second-order perturbation theory using aug cc pvtz basis set. The relative contributions of the conformers have been estimated by solving the vibrational problem according to the large-amplitude vibration model. Based on a set of high resolution of 1D and 2D experiments, complete spectral assignment of all peaks have been performed (including the signals of the diastereomeric protons H2S and H2R). This allows us to get the presentable set of NMR parameters good enough for succeed conformational analysis. The conformational dependences of the most characteristic coupling constants for noradrenalin and its protonated form have been calculated at the FPT DFT B3LYP/6‑311++G(2df,2p) level of theory. The most stable conformers of noradrenalin and its protonated form have g+ and g– configuration. The protonation of noradrenalin causes additional stabilization of g+ form, which is obviously due to strong dipole-dipole interaction of polar groups of this conformer. In reasonable accordance with the data for adrenaline, our data shows, the contribution of the form t with the transoid orientation of oxygen and nitrogen atoms does not exceed 1% for all solvents involved in this study.
- Добавил в систему: Чертков Вячеслав Алексеевич