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

  • 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
  • , and 
  • Peter R. Schreiner*
    Peter R. Schreiner
    Institute of Organic Chemistry, Justus Liebig University, Heinrich-Buff-Ring 17, 35392 Giessen, Germany
    *E-mail: [email protected]
Cite this: J. Org. Chem. 2020, 85, 6, 4441–4447
Publication Date (Web):February 19, 2020
https://doi.org/10.1021/acs.joc.0c00167
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.

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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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    Cited By

    This article is cited by 8 publications.

    1. Long Min, Li-Ping Zhong, Chuang-Chuang Li. Total Synthesis of abeo-Steroids via Cycloaddition Strategy. Accounts of Chemical Research 2023, 56 (17) , 2378-2390. https://doi.org/10.1021/acs.accounts.3c00350
    2. Hai-Tao Zhu, Chun-Miao Liang, Ting-Yan Li, Lin-Yan Li, Rui-Ling Zhang, Jun-Na Wang, Rui-Qing Qi, Jia-Min Zhang, Ruo-Han Yang, Yin-Qi Yang, An-Xi Zhou, Xiaojie Jin, Ni-Ni Zhou. Dual Proton/Silver-Catalyzed Serial (5 + 2)-Cycloaddition and Nazarov Cyclization of (E)-2-Arylidene-3-hydroxyindanones with Conjugated Eneynes: Synthesis of Indanone-Fused Benzo[cd]azulenes. The Journal of Organic Chemistry 2023, 88 (6) , 3409-3423. https://doi.org/10.1021/acs.joc.2c02247
    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
    6. 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
    7. 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
    8. 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