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Regioselective Cu-Catalyzed Hydroboration of 1,3-Disubstituted-1,3-Dienes: Functionalization of Conjugated Dienes Readily Accessible through Ene–Yne Metathesis

  • Ruoshui Xu
    Ruoshui Xu
    Department of Chemistry, University at Buffalo, the State University of New York, Amherst, New York 14260-3000, United States
    More by Ruoshui Xu
  • Laurence N. Rohde Jr.
    Laurence N. Rohde, Jr.
    Department of Chemistry, University at Buffalo, the State University of New York, Amherst, New York 14260-3000, United States
  • , and 
  • Steven T. Diver*
    Steven T. Diver
    Department of Chemistry, University at Buffalo, the State University of New York, Amherst, New York 14260-3000, United States
    *Email: [email protected]
Cite this: ACS Catal. 2022, 12, 11, 6434–6443
Publication Date (Web):May 13, 2022
https://doi.org/10.1021/acscatal.2c01190
Copyright © 2022 American Chemical Society

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    Abstract

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    A regioselective Cu-catalyzed formal hydroboration of 1,3-disubstituted-1,3-dienes is reported. Highly substituted 1,3-dienes produced through catalytic ene–yne metathesis provided substrates for the regioselective hydroboration with variable substituents conveniently introduced from a 1-alkene and a terminal alkyne. For the achiral reaction, the diphosphine 1,2-bis(diphenylphosphino)benzene (dppbz) was used as the ligand. For the enantioselective reaction, EtDuPhos was used as the diphosphine ligand, and good enantioselectivites were obtained in most cases. Control studies showed that the stereoisomeric purity of the 1,3-diene and the Cu(I) source were key variables that led to the highest regioselectivity. In situ NMR experiments and deuterium quenching confirmed the presence of an allyl copper intermediate, which did not exchange with other 1,3-dienes. A proposed model for the regioselectivity is based on the addition of Cu-B to the 1,3-diene where steric effects in the 3,4-addition are more severe than those in the favored 1,2-addition mode. The products were further functionalized and were employed in a dual-catalytic cross-coupling reaction.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acscatal.2c01190.

    • Experimental procedures for the synthesis of 1,3-dienes and for the formal Cu-catalyzed hydroboration, mechanistic experiments, and characterization data for new compounds (PDF)

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    Cited By

    This article is cited by 6 publications.

    1. Liqun Yang, Xiaoyu Wu, Wenkui Lu, Yan Lu, Zhaoguo Zhang. Dirhodium(II)/DPPM Catalyzed 1,2-Hydrosilylation of Conjugated Dienes with Tertiary Silanes. Organic Letters 2024, 26 (11) , 2287-2291. https://doi.org/10.1021/acs.orglett.4c00450
    2. Yong-Yuan Gui, Xiao-Wang Chen, Xiao-Yan Mo, Jun-Ping Yue, Rong Yuan, Yi Liu, Li-Li Liao, Jian-Heng Ye, Da-Gang Yu. Cu-Catalyzed Asymmetric Dicarboxylation of 1,3-Dienes with CO2. Journal of the American Chemical Society 2024, 146 (5) , 2919-2927. https://doi.org/10.1021/jacs.3c14146
    3. Sensheng Liu, Yangbin Liu, Arthur Flaget, Cheng Zhang, Clément Mazet. Cu-Catalyzed Enantioselective Protoboration of 2,3-Disubstituted 1,3-Dienes. Organic Letters 2023, 25 (37) , 6897-6901. https://doi.org/10.1021/acs.orglett.3c02627
    4. Mahesh M. Parsutkar, Subhajit Bhunia, Mayukh Majumder, Remy F. Lalisse, Christopher M. Hadad, T.V. RajanBabu. Ligand Control in Co-Catalyzed Regio- and Enantioselective Hydroboration: Homoallyl Secondary Boronates via Uncommon 4,3-Hydroboration of 1,3-Dienes. Journal of the American Chemical Society 2023, 145 (13) , 7462-7481. https://doi.org/10.1021/jacs.3c00181
    5. Bingru Li, Huayu Liang, Arumugam Vignesh, Xiaoyu Zhou, Yan Liu, Zhuofeng Ke. Updated Progress of the Copper-Catalyzed Borylative Functionalization of Unsaturated Molecules. Molecules 2023, 28 (5) , 2252. https://doi.org/10.3390/molecules28052252
    6. Steven T. Diver, Elise Glickert, Laurence N. Rohde, Thérèse Wild. Stereoconvergent Synthesis of Z ‐1,3‐Disubstituted‐1,3‐Dienes by Uphill Photocatalysis. Chemistry – A European Journal 2023, 29 (1) https://doi.org/10.1002/chem.202202635

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