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Asymmetric Photochemical [2 + 2]-Cycloaddition of Acyclic Vinylpyridines through Ternary Complex Formation and an Uncontrolled Sensitization Mechanism
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    Asymmetric Photochemical [2 + 2]-Cycloaddition of Acyclic Vinylpyridines through Ternary Complex Formation and an Uncontrolled Sensitization Mechanism
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    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2022, 144, 43, 20109–20117
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    https://doi.org/10.1021/jacs.2c09690
    Published October 20, 2022
    Copyright © 2022 American Chemical Society

    Abstract

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    Stereochemical control of photochemical reactions that occur via triplet energy transfer remains a challenge. Suppressing off-catalyst stereorandom reactivity is difficult for highly reactive open-shell intermediates. Strategies for suppressing racemate-producing, off-catalyst pathways have long focused on formation of ground state, substrate-catalyst chiral complexes that are primed for triplet energy transfer via a photocatalyst in contrast to their off-catalyst counterparts. Herein, we describe a strategy where both a chiral catalyst-associated vinylpyridine and a nonassociated, free vinylpyridine substrate can be sensitized by an Ir(III) photocatalyst, yet high levels of diastereo- and enantioselectivity in a [2 + 2] photocycloaddition are achieved through a preferred, highly organized transition state. This mechanistic paradigm is distinct from, yet complementary to current approaches for achieving high levels of stereocontrol in photochemical transformations.

    Copyright © 2022 American Chemical Society

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    CCDC 2195253 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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    This article is cited by 18 publications.

    1. Ye Hu, Qian Liu, Xiang Zhou, Yao Huang, Israel Fernández, Yang Xiong. Lewis-Acid-Promoted Visible-Light-Mediated C(sp3)–H Bond Functionalization of Arylvinylpyridines via Diradical Hydrogen Atom Transfer. Organic Letters 2024, 26 (38) , 8005-8010. https://doi.org/10.1021/acs.orglett.4c02508
    2. Juliette Zanzi, Zachary Pastorel, Carine Duhayon, Elise Lognon, Christophe Coudret, Antonio Monari, Isabelle M. Dixon, Yves Canac, Michael Smietana, Olivier Baslé. Counterion Effects in [Ru(bpy)3](X)2-Photocatalyzed Energy Transfer Reactions. JACS Au 2024, 4 (8) , 3049-3057. https://doi.org/10.1021/jacsau.4c00384
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    8. Yanli Yin, Mengdi You, Xiangtao Li, Zhiyong Jiang. Catalytic asymmetric photocycloaddition reactions mediated by enantioselective radical approaches. Chemical Society Reviews 2025, 108 https://doi.org/10.1039/D5CS00019J
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    11. Dong Tian, Wenshuo Shi, Xin Sun, Xiaowei Zhao, Yanli Yin, Zhiyong Jiang. Catalytic asymmetric [4 + 2] dearomative photocycloadditions of anthracene and its derivatives with alkenylazaarenes. Nature Communications 2024, 15 (1) https://doi.org/10.1038/s41467-024-48982-y
    12. Xintao Gu, Jiahao Shen, Ziyu Xu, Jiaxin Liu, Min Shi, Yin Wei. Visible‐Light‐Mediated Activation of Remote C(sp 3 )−H Bonds by Carbon‐Centered Biradical via Intramolecular 1,5‐ or 1,6‐Hydrogen Atom Transfer. Angewandte Chemie 2024, 136 (38) https://doi.org/10.1002/ange.202409463
    13. Xintao Gu, Jiahao Shen, Ziyu Xu, Jiaxin Liu, Min Shi, Yin Wei. Visible‐Light‐Mediated Activation of Remote C(sp 3 )−H Bonds by Carbon‐Centered Biradical via Intramolecular 1,5‐ or 1,6‐Hydrogen Atom Transfer. Angewandte Chemie International Edition 2024, 63 (38) https://doi.org/10.1002/anie.202409463
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    15. Sermadurai Selvakumar. Synergistic Dual Photoredox and Chiral Hydrogen Bonding Catalysis: Recent Advances. Asian Journal of Organic Chemistry 2023, 12 (10) https://doi.org/10.1002/ajoc.202300374
    16. Lei-Min Zhao. Construction of gel networks via [2+2] photocycloaddition. Journal of Materials Chemistry C 2023, 11 (8) , 2826-2830. https://doi.org/10.1039/D2TC05270A
    17. Ming Xu, Zhijun Wang, Zhaohui Sun, Yizhao Ouyang, Zhengwei Ding, Tao Yu, Liang Xu, Pengfei Li. Diboron(4)‐Catalyzed Remote [3+2] Cycloaddition of Cyclopropanes via Dearomative/Rearomative Radical Transmission through Pyridine. Angewandte Chemie 2022, 134 (52) https://doi.org/10.1002/ange.202214507
    18. Ming Xu, Zhijun Wang, Zhaohui Sun, Yizhao Ouyang, Zhengwei Ding, Tao Yu, Liang Xu, Pengfei Li. Diboron(4)‐Catalyzed Remote [3+2] Cycloaddition of Cyclopropanes via Dearomative/Rearomative Radical Transmission through Pyridine. Angewandte Chemie International Edition 2022, 61 (52) https://doi.org/10.1002/anie.202214507

    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2022, 144, 43, 20109–20117
    Click to copy citationCitation copied!
    https://doi.org/10.1021/jacs.2c09690
    Published October 20, 2022
    Copyright © 2022 American Chemical Society

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