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Theoretical studies on the conformation of saccharides

VII. Structure and stereochemistry of α- and β-d-glucopyranose in solution

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Abstract

The stereochemistry of d-glucopyranose has been studied theoretically in 11 solvents. The stability of the individual conformers in solution has been compared using a method in which the total energy is divided into the energy of an isolated molecule and the solvation energy. The structure and the energy of the isolated molecule have been estimated by geometry optimization using the PCILO quantum chemical method. The solvation energy consists of electrostatic, dispersion, and cavity terms which have been determined from calculated properties of the solute and physiochemical properties of the solvents. The influence of the solvent on rotation of the individual pendant groups and the stability of anomers have been investigated. The calculated composition of the anomeric mixture of d-glucopyranose in various solvents at 25°C (e.g., in pyridine 49% is α-anomer, in dimethyl sulfoxide 46%, and in water 32%) is in good agreement with the available experimental data and clearly demonstrates that the solvation properties of α- and β-d-glucopyranose differ. Based on the calculated abundances of anomers the magnitude of the anomeric effect has been estimated and compared with the results of corresponding calculations on other compounds.

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Author notes

  1. Tibor Kožár

    Present address: Institute of Experimental Physics, Slovak Academy of Sciences, CS-040 01, Košice, Czechoslovakia

Authors and Affiliations

  1. Institute of Chemistry, Slovak Academy of Sciences, CS-842 38, Bratislava, Czechoslovakia

    Igor Tvaroška & Tibor Kožár

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  1. Igor Tvaroška
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  2. Tibor Kožár
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Tvaroška, I., Kožár, T. Theoretical studies on the conformation of saccharides. Theoret. Chim. Acta 70, 99–114 (1986). https://doi.org/10.1007/BF00532207

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  • DOI: https://doi.org/10.1007/BF00532207

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