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Regioselective Hydroalkylation of Vinyl- and Allylsilanes as Well as Vinylgermanes under Ni–H Catalysis
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    Regioselective Hydroalkylation of Vinyl- and Allylsilanes as Well as Vinylgermanes under Ni–H Catalysis
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    Organic Letters

    Cite this: Org. Lett. 2023, 25, 28, 5319–5323
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    https://doi.org/10.1021/acs.orglett.3c01881
    Published July 7, 2023
    Copyright © 2023 The Authors. Published by American Chemical Society
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    Abstract

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    A Ni–H-catalyzed hydroalkylation of vinylsilanes and -germanes as well as allylsilanes with unactivated alkyl iodides is reported. Unlike related reactions of styrene or vinyl boronate esters, the addition across the C–C double bond proceeds with anti-Markovnikov selectivity to deliver the linear regioisomer. Mechanistic control experiments support a radical mechanism, and a competition experiment reveals that the chemoselectivity is in favor of the vinyl over the allyl group.

    Copyright © 2023 The Authors. Published by American Chemical Society

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    Supporting Information

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    Cited By

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    This article is cited by 10 publications.

    1. Daniel Brösamlen, Martin Oestreich. Asymmetric Transition-Metal-Catalyzed Hydrofunctionalization of Alkenylmetalloids (B, Si, and Ge). ACS Catalysis 2026, 16 (7) , 6198-6214. https://doi.org/10.1021/acscatal.6c00700
    2. Bincy Chindan, Anagha Syam, Thayalan Rajeshkumar, Venkadesh Balakrishnan, Laurent Maron, Ramesh Rasappan. Ligand Controlled Regiodivergent Synthesis of α-Tertiary and Quaternary Alkyl-Alkoxysilanes. ACS Catalysis 2025, 15 (16) , 14505-14513. https://doi.org/10.1021/acscatal.5c03042
    3. Xue-Song Wang, Yu-Jie Zhang, Jian Cao, Li-Wen Xu. Photoinduced Palladium-Catalyzed Radical Germylative Arylation of Alkenes with Chlorogermanes. The Journal of Organic Chemistry 2024, 89 (17) , 12848-12852. https://doi.org/10.1021/acs.joc.4c01456
    4. Daniel Brösamlen, Martin Oestreich. Ligand-Controlled On–Off Switch of a Silicon-Tethered Directing Group Enabling the Regiodivergent Hydroalkylation of Vinylsilanes under Ni–H Catalysis. Organic Letters 2024, 26 (5) , 977-982. https://doi.org/10.1021/acs.orglett.3c03799
    5. Roxane Arnaudy, Faycel Djebbar, Adrien Tintar, Guillaume Lefèvre. Bis-Alkenyl Compounds from Group XIV Elements (Si, Ge, Sn): Synthesis, Reactivity, and Applications. Synthesis 2025, 57 (21) , 3127-3146. https://doi.org/10.1055/a-2650-0599
    6. Emilio G. A. Acuña-Bolomey, Martin Oestreich. Nickel-Catalyzed Enantioconvergent C(sp3)–C(sp3) Cross-Coupling between α-Iodogermanes and Alkylzinc Reagents. Synthesis 2025, 57 (21) , 3273-3282. https://doi.org/10.1055/a-2643-6539
    7. Daniel Brösamlen, Martin Oestreich. Directing Effects of Silyl and Germyl Groups in Transition‐Metal‐Catalyzed Allylic Substitution. Chemistry – A European Journal 2025, 31 (58) https://doi.org/10.1002/chem.202502196
    8. Haifeng Chen, Magnus Rueping. Facile, general allylation of unactivated alkyl halides via electrochemically enabled radical-polar crossover. Chemical Science 2025, 16 (15) , 6317-6324. https://doi.org/10.1039/D4SC07923J
    9. Itaru Suzuki, Ikuya Shibata. Allylsilanes, Allyltins, and Related Compounds. 2025, 62-138. https://doi.org/10.1016/B978-0-323-96025-0.00069-7
    10. Daniel Brösamlen, Martin Oestreich. Ni–H-Catalyzed Chemo- and Regioselective Hydroarylation of Vinylsilanes. Synthesis 2024, 56 (20) , 3160-3166. https://doi.org/10.1055/a-2367-2434
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    Organic Letters

    Cite this: Org. Lett. 2023, 25, 28, 5319–5323
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.orglett.3c01881
    Published July 7, 2023
    Copyright © 2023 The Authors. Published by American Chemical Society
    Request reuse permissions

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