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Synthesis and Conformational Analysis of Parent Perhydroazulenes Reveal an Energetically Preferred cis Ring Fusion

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    Synthesis and Conformational Analysis of Parent Perhydroazulenes Reveal an Energetically Preferred cis Ring Fusion
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    • Fumito Saito
      Fumito Saito
      Institute of Organic Chemistry, Justus Liebig University, Heinrich-Buff-Ring 17, 35392 Giessen, Germany
      More by Fumito Saito
    • Jonathan Becker
      Jonathan Becker
      Institute of Inorganic and Analytical Chemistry, Justus Liebig University, Heinrich-Buff-Ring 17, 35392 Giessen, Germany
      More by Jonathan Becker
    • Peter R. Schreiner*
      Peter R. Schreiner
      Institute of Organic Chemistry, Justus Liebig University, Heinrich-Buff-Ring 17, 35392 Giessen, Germany
      *E-mail: [email protected]
      More by Peter R. Schreiner
      Orcidhttp://orcid.org/0000-0002-3608-5515
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    The Journal of Organic Chemistry

    Cite this: J. Org. Chem. 2020, 85, 6, 4441–4447
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    https://doi.org/10.1021/acs.joc.0c00167
    Published February 19, 2020
    Copyright © 2020 American Chemical Society
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    Abstract

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    Perhydroazulenes are common structural motifs in various terpene natural products. Herein, we present the synthesis of parent cis- and trans-perhydroazulenes. Conformational analysis performed with density functional theory (DFT, e.g., B3LYP, M06-2X) and MP2 geometry optimizations with a cc-pVTZ basis set, followed by CCSD(T)/cc-pVTZ single-point energy computations reveals that the cis isomer is 0.7 kcal mol–1 more stable than the trans isomer. Steric and torsional strains present in the trans isomer are responsible for this unexpected relative cis/trans stability.

    Copyright © 2020 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.joc.0c00167.

    • 1H and 13C{1H} NMR spectra for all new compounds; X-ray crystallographic data and Cartesian coordinates for optimized structures of cycloheptane; trans- and cis-1,2-dimethylcycloheptanes, 1c, and 1t (PDF)

    • X-ray crystallographic data for compound 5 (CIF)

    • X-ray crystallographic data for compound 11 (CIF)

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    This article is cited by 11 publications.

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    3. Christian J. Oswood, David W. C. MacMillan. Selective Isomerization via Transient Thermodynamic Control: Dynamic Epimerization of trans to cis Diols. Journal of the American Chemical Society 2022, 144 (1) , 93-98. https://doi.org/10.1021/jacs.1c11552
    4. Fumito Saito, Dennis Gerbig, Jonathan Becker, Peter R. Schreiner. Breaking the Symmetry of a Meso Compound by Isotopic Substitution: Synthesis and Stereochemical Assignment of Monodeuterated cis-Perhydroazulene. Organic Letters 2021, 23 (1) , 113-117. https://doi.org/10.1021/acs.orglett.0c03795
    5. Fumito Saito, Dennis Gerbig, Jonathan Becker, Peter R. Schreiner. Absolute Configuration of trans-Perhydroazulene. Organic Letters 2020, 22 (10) , 3895-3899. https://doi.org/10.1021/acs.orglett.0c01184
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    9. Shihang Wang, Lin Wang, Fenglei Li, Fang Bai. DeepSA: a deep-learning driven predictor of compound synthesis accessibility. Journal of Cheminformatics 2023, 15 (1) https://doi.org/10.1186/s13321-023-00771-3
    10. James Burrows, Shogo Kamo, Kazunori Koide. Scalable Birch reduction with lithium and ethylenediamine in tetrahydrofuran. Science 2021, 374 (6568) , 741-746. https://doi.org/10.1126/science.abk3099
    11. Fumito Saito, Peter R. Schreiner. Determination of the Absolute Configurations of Chiral Alkanes – An Analysis of the Available Tools. European Journal of Organic Chemistry 2020, 2020 (40) , 6328-6339. https://doi.org/10.1002/ejoc.202000711
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    The Journal of Organic Chemistry

    Cite this: J. Org. Chem. 2020, 85, 6, 4441–4447
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.joc.0c00167
    Published February 19, 2020
    Copyright © 2020 American Chemical Society
    Request reuse permissions

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