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Conformational and reactivity study of dithiophenyl-fucosyl ketals with theoretical chemical methods

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Abstract

Carbohydrates can be used as substrates to synthesize new complex molecules; these molecules contain several chiral centers that can be used in organic synthesis. d-Fucose diphenyl thioacetal reacts differentially with acetone, and this paper describes a study of the mechanism of this reaction using theoretical chemistry methods. The conformer distribution was studied using a Monte Carlo method for the reaction products, and the obtained conformers were validated by calculating the hydrogen spin-spin coupling constants with the DFT/B3LYP/DGDZVP method. Results agreed with the experimental coupling constants with an adequate root mean squared deviation. The free energies and enthalpies of formation of the resulting global minimum conformers were calculated with the same method and with the thermochemical compound method CBS-4 M. This technique, combined with the conformational analysis, allowed comparison of the formation enthalpies of the compounds involved in this reaction, and, with this information, we can postulate the correct reaction pathway.

Reaction pathway

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Acknowledgments

Computational resources were provided by the Dirección General de Servicios de Cómputo Académico, Universidad Nacional Autónoma de México. Partial financial support from CONACYT, Mexico (CB-167952), from Centro de Investigación y de Estudios Avanzados del Instituto Politécnico Nacional, from Universidad Autónoma de la Ciudad de México, and from Universidad Michoacana de San Nicolás de Hidalgo is also acknowledged.

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Authors and Affiliations

  1. Programa de Posgrado en Farmacología, Centro de Investigación y de Estudios Avanzados del Instituto Politécnico Nacional, Mexico, Mexico

    Angel E. Bañuelos-Hernandez

  2. Instituto de Investigaciones Químico-Biológicas, Universidad Michoacana de San Nicolás de Hidalgo, Apartado 137, Morelia, Michoacán, 58000, Mexico

    Hugo A. García-Gutiérrez

  3. Departamento de Farmacia, Facultad de Química, Universidad Nacional Autónoma de México, Ciudad de México, 04510, Mexico

    Mabel Fragoso-Serrano

  4. Colegio de Ciencia y Humanidades, Universidad Autónoma de la Ciudad de México, Ciudad de México, 09620, Mexico

    José Alberto Mendoza-Espinoza

Authors
  1. Angel E. Bañuelos-Hernandez
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  2. Hugo A. García-Gutiérrez
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  3. Mabel Fragoso-Serrano
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  4. José Alberto Mendoza-Espinoza
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Corresponding author

Correspondence to José Alberto Mendoza-Espinoza.

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Bañuelos-Hernandez, A.E., García-Gutiérrez, H.A., Fragoso-Serrano, M. et al. Conformational and reactivity study of dithiophenyl-fucosyl ketals with theoretical chemical methods. J Mol Model 22, 212 (2016). https://doi.org/10.1007/s00894-016-3079-9

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