ACS Publications. Most Trusted. Most Cited. Most Read
Dynamic Intermediates in the Radical Cation Diels–Alder Cycloaddition: Lifetime and Suprafacial Stereoselectivity

OR SEARCH CITATIONS

My Activity
Publications

Figure 1Loading Img
Download Hi-Res ImageDownload to MS-PowerPointCite This:Org. Lett. 2018, 20, 10, 2821-2825
    Letter

    Dynamic Intermediates in the Radical Cation Diels–Alder Cycloaddition: Lifetime and Suprafacial Stereoselectivity
    Click to copy article linkArticle link copied!

    Other Access OptionsSupporting Information (2)

    Organic Letters

    Cite this: Org. Lett. 2018, 20, 10, 2821–2825
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.orglett.8b00737
    Published May 9, 2018
    Copyright © 2018 American Chemical Society
    Request reuse permissions

    Abstract

    Click to copy section linkSection link copied!
    Abstract Image

    Cation radical Diels–Alder cycloadditions proceed via an acyclic intermediate that exists on a flat region of the potential energy surface. Competition between cyclization and C–C bond rotation results in varying levels of suprafacial stereoselectivity. Quasi-classical trajectories were used to explore reaction dynamics on this surface. Even though there is no discernible energy barrier toward cyclization, a dynamically stepwise process is found, for which the acyclic intermediate is found to reside for several hundreds of femtoseconds. In a small number of cases, exceptionally long lifetimes (>1000 fs) are found, leading to a loss of alkene stereochemistry.

    Copyright © 2018 American Chemical Society

    Subjects

    what are subjects

    Read this article

    To access this article, please review the available access options below.

    Get instant access

    Purchase Access

    Read this article for 48 hours. Check out below using your ACS ID or as a guest.

    Recommended

    Access through Your Institution

    You may have access to this article through your institution.

    Your institution does not have access to this content. Add or change your institution or let them know you’d like them to include access.

    Supporting Information

    Click to copy section linkSection link copied!

    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.orglett.8b00737.

    • Cartesian coordinates, absolute energies, and imaginary frequencies of all transition structures reported; Gibbs energy profiles, scripts, and BOMD settings (PDF)

    • Supporting videos (ZIP)

    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

    Cited By

    Click to copy section linkSection link copied!
    Citation Statements
    Explore this article's citation statements on scite.ai
    powered by  Scite

    This article is cited by 22 publications.

    1. Maoping Pu, Christian D.-T. Nielsen, Erdem Senol, Theresa Sperger, Franziska Schoenebeck. Post-Transition-State Dynamic Effects in the Transmetalation of Pd(II)-F to Pd(II)-CF3. JACS Au 2024, 4 (1) , 263-275. https://doi.org/10.1021/jacsau.3c00724
    2. Zhi-Xin Qin, Matthew Tremblay, Xin Hong, Zhongyue J. Yang. Entropic Path Sampling: Computational Protocol to Evaluate Entropic Profile along a Reaction Path. The Journal of Physical Chemistry Letters 2021, 12 (43) , 10713-10719. https://doi.org/10.1021/acs.jpclett.1c03116
    3. Jed M. Burns, Eric D. Boittier. Pathway Bifurcation in the (4 + 3)/(5 + 2)-Cycloaddition of Butadiene and Oxidopyrylium Ylides: The Significance of Molecular Orbital Isosymmetry. The Journal of Organic Chemistry 2019, 84 (10) , 5997-6005. https://doi.org/10.1021/acs.joc.8b03236
    4. Kaii Nakayama, Naoya Maeta, Genki Horiguchi, Hidehiro Kamiya, Yohei Okada. Radical Cation Diels–Alder Reactions by TiO2 Photocatalysis. Organic Letters 2019, 21 (7) , 2246-2250. https://doi.org/10.1021/acs.orglett.9b00526
    5. Nilangshu Mandal, Ayan Datta. Gold(I)-Catalyzed Intramolecular Diels–Alder Reaction: Evolution of Trappable Intermediates via Asynchronous Transition States. The Journal of Organic Chemistry 2018, 83 (18) , 11167-11177. https://doi.org/10.1021/acs.joc.8b01752
    6. Maryam Mousavi-Ebadia, Javad Safaei-Ghomi, Masoumeh Jadidi Nejad. Synthesis of thiopyran derivatives via [4 + 2] cycloaddition reactions. RSC Advances 2025, 15 (14) , 11160-11188. https://doi.org/10.1039/D5RA01222H
    7. Reyhan Güdük, Niklas Kehl, Chiara Stavagna, Michael J. Tilby, Oliver Turner, Alessandro Ruffoni, Henry P. Caldora, Daniele Leonori. A three-step strategy for the conversion of pyridines into benzonitriles. Nature Synthesis 2025, 96 https://doi.org/10.1038/s44160-025-00759-x
    8. Haruka Morizumi, Kaii Nakayama, Yoshikazu Kitano, Yohei Okada. Redox-Tag-Guided Radical Cation Diels–Alder Reactions: Use of Enol Ethers as Dienophiles. Synlett 2024, 35 (03) , 362-366. https://doi.org/10.1055/a-2161-9607
    9. Ranjana Bisht, Mihai V. Popescu, Zhen He, Ameer M. Ibrahim, Giacomo E. M. Crisenza, Robert S. Paton, David J. Procter. Metal‐Free Arylation of Benzothiophenes at C4 by Activation as their Benzothiophene S ‐Oxides. Angewandte Chemie 2023, 135 (29) https://doi.org/10.1002/ange.202302418
    10. Ranjana Bisht, Mihai V. Popescu, Zhen He, Ameer M. Ibrahim, Giacomo E. M. Crisenza, Robert S. Paton, David J. Procter. Metal‐Free Arylation of Benzothiophenes at C4 by Activation as their Benzothiophene S ‐Oxides. Angewandte Chemie International Edition 2023, 62 (29) https://doi.org/10.1002/anie.202302418
    11. Meire Y. Kawamura, Juan V. Alegre‐Requena, Thaís M. Barbosa, Cláudio F. Tormena, Robert S. Paton, Marco A. B. Ferreira. Mechanistic Aspects on [3+2] Cycloaddition (32CA) Reactions of Azides to Nitroolefins: A Computational and Kinetic Study. Chemistry – A European Journal 2022, 28 (69) https://doi.org/10.1002/chem.202202294
    12. Daniele Loco, Isabelle Chataigner, Jean‐Philip Piquemal, Riccardo Spezia. Efficient and Accurate Description of Diels‐Alder Reactions Using Density Functional Theory**. ChemPhysChem 2022, 23 (18) https://doi.org/10.1002/cphc.202200349
    13. Pascal Vermeeren, Trevor A. Hamlin, F. Matthias Bickelhaupt. How Ionization Catalyzes Diels‐Alder Reactions. Chemistry – A European Journal 2022, 28 (40) https://doi.org/10.1002/chem.202200987
    14. Kaii Nakayama, Hidehiro Kamiya, Yohei Okada. Radical cation Diels–Alder reactions of arylidene cycloalkanes. Beilstein Journal of Organic Chemistry 2022, 18 , 1100-1106. https://doi.org/10.3762/bjoc.18.112
    15. A. F. Parsons, T. F. Parsons. Radical Reactions. 2021, 553-591. https://doi.org/10.1002/9781119531975.ch14
    16. Shi Jun Ang, Wujie Wang, Daniel Schwalbe-Koda, Simon Axelrod, Rafael Gómez-Bombarelli. Active learning accelerates ab initio molecular dynamics on reactive energy surfaces. Chem 2021, 7 (3) , 738-751. https://doi.org/10.1016/j.chempr.2020.12.009
    17. Xinglong Zhang, Robert S. Paton. Stereoretention in styrene heterodimerisation promoted by one-electron oxidants. Chemical Science 2020, 11 (34) , 9309-9324. https://doi.org/10.1039/D0SC03059G
    18. Oliver T Unke, Debasish Koner, Sarbani Patra, Silvan Käser, Markus Meuwly. High-dimensional potential energy surfaces for molecular simulations: from empiricism to machine learning. Machine Learning: Science and Technology 2020, 1 (1) , 013001. https://doi.org/10.1088/2632-2153/ab5922
    19. Uxía Rivero, Oliver T. Unke, Markus Meuwly, Stefan Willitsch. Reactive atomistic simulations of Diels-Alder reactions: The importance of molecular rotations. The Journal of Chemical Physics 2019, 151 (10) https://doi.org/10.1063/1.5114981
    20. Atsushi Ozaki, Yusuke Yamaguchi, Yohei Okada, Kazuhiro Chiba. Radical Cation Diels‐Alder Reactions of Non‐Conjugated Alkenes as Dienophiles by Electrocatalysis. Chinese Journal of Chemistry 2019, 37 (6) , 561-564. https://doi.org/10.1002/cjoc.201900054
    21. Yohei Okada, Kazuhiro Chiba. Redox Tag-Guided Radical Cation Cycloadditions. Journal of Synthetic Organic Chemistry, Japan 2019, 77 (5) , 442-451. https://doi.org/10.5059/yukigoseikyokaishi.77.442
    22. Christian D.-T. Nielsen, Wouter J. Mooij, David Sale, Henry S. Rzepa, Jordi Burés, Alan C. Spivey. Reversibility and reactivity in an acid catalyzed cyclocondensation to give furanochromanes – a reaction at the ‘oxonium-Prins’ vs. ‘ ortho -quinone methide cycloaddition’ mechanistic nexus. Chemical Science 2019, 10 (2) , 406-412. https://doi.org/10.1039/C8SC04302G
    Download PDF
    Go to Organic Letters
    Get e-Alerts
    Get e-Alerts

    Organic Letters

    Cite this: Org. Lett. 2018, 20, 10, 2821–2825
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.orglett.8b00737
    Published May 9, 2018
    Copyright © 2018 American Chemical Society
    Request reuse permissions

    Article Views

    1994

    Altmetric

    -

    Citations

    22
    Learn about these metrics

    Article Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.

    Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.

    The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated.