American Journal of Quantum Chemistry and Molecular Spectroscopy

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Configurational and Conformational Analysis of 5-deoxy-5-iodo-α,β-D-ribose with 3-Sphere Approach

Received: 7 March 2023    Accepted: 27 March 2023    Published: 11 April 2023
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Abstract

Configurational and conformational analysis with 3-Sphere approach on selective iodination of α, β-methyl D-ribofuranose (2-α:2-β) with iodotriphenilphosphonium iodide complex [Ph3P+I]I- generated in situ, under RT, reflux, microwave and sonochemistry. Introduction of the unit and hypersphere trigonometric equations, under Hopf fibration and Lie algebra theories, on Lambert-Wu methods enable calculation of the dihedral angles from NMR data (13C chemical shift, vicinal coupling constant 3JHH[Hz]) and the ratio of anomers. The conformation/configuration at anomeric position is cis: trans with axial:axial 3-α:3-β (3JH1H2 3 or 4.5:0[Hz]) or equatorial:axial 3-α:3-β (3JH1H2 6 or 4.5:0[Hz]) as state based on dihedral angles θH1H2[deg], recorded carbon chemical shift δCn[deg] and VISION molecular models. The conformation of 3-β anomer is 3E, and in case of 3-α anomer 3E on Altona’s map, the last having the succession of sign (+, -, -) with θH3H4α trans-ee, or alternatively 32T conformation having the succession of sign (-, +, -) with θH3H4α trans-aa. An equilibrium between 3E α and 32T α was confirmed by 3JH1H2 of 4.5[Hz], i.e. negative θH1H2α with 32T and equatorial OCH3, or positive θH1H2α with 3E and axial OCH3. The APT experiment (attached proton test) demonstrated the formation of tetrahydro 2H-pyran-2-ol as side product after selective iodination of methyl 5-deoxy-β-D-ribofuranoside 2-β.

DOI 10.11648/j.ajqcms.20230701.11
Published in American Journal of Quantum Chemistry and Molecular Spectroscopy (Volume 7, Issue 1, June 2023)
Page(s) 1-8
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This is an Open Access article, distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution and reproduction in any medium or format, provided the original work is properly cited.

Copyright

Copyright © The Author(s), 2024. Published by Science Publishing Group

Keywords

3-Sphere, Dihedral Angles, Configuration, Conformation, Selective Iodination

References
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    Carmen-Irena Mitan, Emeric Bartha, Anca Hirtopeanu, Carmen Stavarache, Constantin Draghici, et al. (2023). Configurational and Conformational Analysis of 5-deoxy-5-iodo-α,β-D-ribose with 3-Sphere Approach. American Journal of Quantum Chemistry and Molecular Spectroscopy, 7(1), 1-8. https://doi.org/10.11648/j.ajqcms.20230701.11

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    ACS Style

    Carmen-Irena Mitan; Emeric Bartha; Anca Hirtopeanu; Carmen Stavarache; Constantin Draghici, et al. Configurational and Conformational Analysis of 5-deoxy-5-iodo-α,β-D-ribose with 3-Sphere Approach. Am. J. Quantum Chem. Mol. Spectrosc. 2023, 7(1), 1-8. doi: 10.11648/j.ajqcms.20230701.11

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    AMA Style

    Carmen-Irena Mitan, Emeric Bartha, Anca Hirtopeanu, Carmen Stavarache, Constantin Draghici, et al. Configurational and Conformational Analysis of 5-deoxy-5-iodo-α,β-D-ribose with 3-Sphere Approach. Am J Quantum Chem Mol Spectrosc. 2023;7(1):1-8. doi: 10.11648/j.ajqcms.20230701.11

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  • @article{10.11648/j.ajqcms.20230701.11,
      author = {Carmen-Irena Mitan and Emeric Bartha and Anca Hirtopeanu and Carmen Stavarache and Constantin Draghici and Miron Teodor Caproiu and Maria Maganu and Petru Filip},
      title = {Configurational and Conformational Analysis of 5-deoxy-5-iodo-α,β-D-ribose with 3-Sphere Approach},
      journal = {American Journal of Quantum Chemistry and Molecular Spectroscopy},
      volume = {7},
      number = {1},
      pages = {1-8},
      doi = {10.11648/j.ajqcms.20230701.11},
      url = {https://doi.org/10.11648/j.ajqcms.20230701.11},
      eprint = {https://article.sciencepublishinggroup.com/pdf/10.11648.j.ajqcms.20230701.11},
      abstract = {Configurational and conformational analysis with 3-Sphere approach on selective iodination of α, β-methyl D-ribofuranose (2-α:2-β) with iodotriphenilphosphonium iodide complex [Ph3P+I]I- generated in situ, under RT, reflux, microwave and sonochemistry. Introduction of the unit and hypersphere trigonometric equations, under Hopf fibration and Lie algebra theories, on Lambert-Wu methods enable calculation of the dihedral angles from NMR data (13C chemical shift, vicinal coupling constant 3JHH[Hz]) and the ratio of anomers. The conformation/configuration at anomeric position is cis: trans with axial:axial 3-α:3-β (3JH1H2 3 or 4.5:0[Hz]) or equatorial:axial 3-α:3-β (3JH1H2 6 or 4.5:0[Hz]) as state based on dihedral angles θH1H2[deg], recorded carbon chemical shift δCn[deg] and VISION molecular models. The conformation of 3-β anomer is 3E, and in case of 3-α anomer 3E on Altona’s map, the last having the succession of sign (+, -, -) with θH3H4α trans-ee, or alternatively 32T conformation having the succession of sign (-, +, -) with θH3H4α trans-aa. An equilibrium between 3E α and 32T α was confirmed by 3JH1H2 of 4.5[Hz], i.e. negative θH1H2α with 32T and equatorial OCH3, or positive θH1H2α with 3E and axial OCH3. The APT experiment (attached proton test) demonstrated the formation of tetrahydro 2H-pyran-2-ol as side product after selective iodination of methyl 5-deoxy-β-D-ribofuranoside 2-β.},
     year = {2023}
    }
    

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  • TY  - JOUR
    T1  - Configurational and Conformational Analysis of 5-deoxy-5-iodo-α,β-D-ribose with 3-Sphere Approach
    AU  - Carmen-Irena Mitan
    AU  - Emeric Bartha
    AU  - Anca Hirtopeanu
    AU  - Carmen Stavarache
    AU  - Constantin Draghici
    AU  - Miron Teodor Caproiu
    AU  - Maria Maganu
    AU  - Petru Filip
    Y1  - 2023/04/11
    PY  - 2023
    N1  - https://doi.org/10.11648/j.ajqcms.20230701.11
    DO  - 10.11648/j.ajqcms.20230701.11
    T2  - American Journal of Quantum Chemistry and Molecular Spectroscopy
    JF  - American Journal of Quantum Chemistry and Molecular Spectroscopy
    JO  - American Journal of Quantum Chemistry and Molecular Spectroscopy
    SP  - 1
    EP  - 8
    PB  - Science Publishing Group
    SN  - 2994-7308
    UR  - https://doi.org/10.11648/j.ajqcms.20230701.11
    AB  - Configurational and conformational analysis with 3-Sphere approach on selective iodination of α, β-methyl D-ribofuranose (2-α:2-β) with iodotriphenilphosphonium iodide complex [Ph3P+I]I- generated in situ, under RT, reflux, microwave and sonochemistry. Introduction of the unit and hypersphere trigonometric equations, under Hopf fibration and Lie algebra theories, on Lambert-Wu methods enable calculation of the dihedral angles from NMR data (13C chemical shift, vicinal coupling constant 3JHH[Hz]) and the ratio of anomers. The conformation/configuration at anomeric position is cis: trans with axial:axial 3-α:3-β (3JH1H2 3 or 4.5:0[Hz]) or equatorial:axial 3-α:3-β (3JH1H2 6 or 4.5:0[Hz]) as state based on dihedral angles θH1H2[deg], recorded carbon chemical shift δCn[deg] and VISION molecular models. The conformation of 3-β anomer is 3E, and in case of 3-α anomer 3E on Altona’s map, the last having the succession of sign (+, -, -) with θH3H4α trans-ee, or alternatively 32T conformation having the succession of sign (-, +, -) with θH3H4α trans-aa. An equilibrium between 3E α and 32T α was confirmed by 3JH1H2 of 4.5[Hz], i.e. negative θH1H2α with 32T and equatorial OCH3, or positive θH1H2α with 3E and axial OCH3. The APT experiment (attached proton test) demonstrated the formation of tetrahydro 2H-pyran-2-ol as side product after selective iodination of methyl 5-deoxy-β-D-ribofuranoside 2-β.
    VL  - 7
    IS  - 1
    ER  - 

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Author Information
  • “C. D. Nenitescu” Institute of Organic and Supramolecular Chemistry, Splaiul Independentei 202B, Bucharest, Romania

  • “C. D. Nenitescu” Institute of Organic and Supramolecular Chemistry, Splaiul Independentei 202B, Bucharest, Romania

  • “C. D. Nenitescu” Institute of Organic and Supramolecular Chemistry, Splaiul Independentei 202B, Bucharest, Romania

  • “C. D. Nenitescu” Institute of Organic and Supramolecular Chemistry, Splaiul Independentei 202B, Bucharest, Romania

  • “C. D. Nenitescu” Institute of Organic and Supramolecular Chemistry, Splaiul Independentei 202B, Bucharest, Romania

  • “C. D. Nenitescu” Institute of Organic and Supramolecular Chemistry, Splaiul Independentei 202B, Bucharest, Romania

  • “C. D. Nenitescu” Institute of Organic and Supramolecular Chemistry, Splaiul Independentei 202B, Bucharest, Romania

  • “C. D. Nenitescu” Institute of Organic and Supramolecular Chemistry, Splaiul Independentei 202B, Bucharest, Romania

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