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Evaluation of the effect of iminium intermediates on the stereoselectivity of the Biginelli reaction involving hydroxyproline-containing podands

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Abstract

The results are presented of a theoretical study on assessment of the stereoselectivity of processes aimed at increasing the enantiomeric excess of chiral pyrimidinones, products of the Biginelli reaction. The effects of hydroxyproline-containing podands used as chiral inductors, viz., the influence of the base or salt forms and of the oxyethylene chain length in the stage of formation of iminium intermediates of the Biginelli reaction are considered. A methodology is proposed for modeling a multicomponent reaction mixture by the molecular dynamics method. The strategy proved itself in quantitative assessment of the stereoselectivity of the approach of urea molecule to the iminium stereoisomers under the conditions of a simulated diffusion stage of the reaction. The energy maps constructed in the polar coordinates make it possible to visually assess the preference of the reagent approach to the different diastereotopic sides.

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Authors and Affiliations

  1. South Ural State University, 76 prosp. Lenina, 454080, Chelyabinsk, Russian Federation

    O. S. Borodina & E. V. Bartashevich

  2. I. Ya. Postovsky Institute of Organic Synthesis, Ural Branch of the Russian Academy of Sciences, 22/20 ul. S. Kovalevskoi, 620108, Ekaterinburg, Russian Federation

    I. G. Ovchinnikova, O. V. Fedorova & G. L. Rusinov

  3. Ural Federal University named after the first President of Russia B. N. Yeltsin, 19 ul. Mira, 620002, Ekaterinburg, Russian Federation

    G. L. Rusinov

Authors
  1. O. S. Borodina
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  2. E. V. Bartashevich
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  3. I. G. Ovchinnikova
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  4. O. V. Fedorova
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  5. G. L. Rusinov
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Correspondence to O. S. Borodina.

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Additional information

This work was carried out using the equipment of the “Spectroscopy and Analysis of Organic Compounds” Center for Joint Use at the I. Ya. Postovsky Institute of Organic Synthesis, Ural Branch of the Russian Academy of Sciences.

This work was financially supported by the Ministry of Science and Higher Education of the Russian Federation (Contract No. 075-15-2020-777) and within the framework of the State Assignment No. FUWM-2024-0009.

No human or animal subjects were used in this research.

Based on the materials of the VI International Conference “Modern Synthetic Methodologies for Creating Drugs and Functional Materials” (MOSM 2022) (November 7–11, 2022, Ekaterinburg, Russia).

Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, Vol. 72, No. 8, pp. 1767–1780, August, 2023.

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Borodina, O.S., Bartashevich, E.V., Ovchinnikova, I.G. et al. Evaluation of the effect of iminium intermediates on the stereoselectivity of the Biginelli reaction involving hydroxyproline-containing podands. Russ Chem Bull 72, 1767–1780 (2023). https://doi.org/10.1007/s11172-023-3959-y

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  • DOI: https://doi.org/10.1007/s11172-023-3959-y

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