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Atropisomeric Phosphine Ligands Bearing C–N Axial Chirality: Applications in Enantioselective Suzuki–Miyaura Cross-Coupling Towards the Assembly of Tetra-ortho-Substituted Biaryls

  • Kin Boon Gan
    Kin Boon Gan
    State Key Laboratory of Synthetic Chemistry and Department of Chemistry, The Chinese University of Hong Kong, Shatin, New Territories, Hong Kong 999077, China
    More by Kin Boon Gan
  • Rong-Lin Zhong*
    Rong-Lin Zhong
    State Key Laboratory of Synthetic Chemistry and Department of Chemistry, The Chinese University of Hong Kong, Shatin, New Territories, Hong Kong 999077, China
    Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, College of Chemistry, Jilin University, Changchun 130023, China
    *Email: [email protected]
  • Zhen-Wei Zhang*
    Zhen-Wei Zhang
    State Key Laboratory of Synthetic Chemistry and Department of Chemistry, The Chinese University of Hong Kong, Shatin, New Territories, Hong Kong 999077, China
    College of Pharmacy, Guangxi Zhuang Yao Medicine Center of Engineering and Technology, Guangxi University of Chinese Medicine, Nanning, Guangxi 530200, China
    *Email: [email protected]
  • , and 
  • Fuk Yee Kwong*
    Fuk Yee Kwong
    State Key Laboratory of Synthetic Chemistry and Department of Chemistry, The Chinese University of Hong Kong, Shatin, New Territories, Hong Kong 999077, China
    *Email: [email protected]
Cite this: J. Am. Chem. Soc. 2022, 144, 32, 14864–14873
Publication Date (Web):August 3, 2022
https://doi.org/10.1021/jacs.2c06240
Copyright © 2022 American Chemical Society

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    Abstract

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    Biaryl phosphines bearing C(Ar)–C(Ar) axial chirality are commonly known and have been successfully applied in many asymmetric catalyses. Nevertheless, the development of a chiral ligand having an axially chiral C(Ar)–N backbone remains elusive due to its undesirable less restricted rotational barrier. In fact, it is highly attractive to overcome this challenge in ligand development as the incorporation of an N-donor component at the chiral axis is more favorable toward the transient metal coordination, and thus, a better outcome of stereocommunication is anticipated to the approaching substrates. Herein, we present a rational design of a new collection of chiral phosphines featuring a C–N axial chirality and their applications in enantioselective Suzuki–Miyaura cross-coupling for accessing highly steric hindered tetra-ortho-substituted biaryls (26 examples up to 98:2 er). It is worth noting that the embodied carbazolyl framework is crucial to succeed the reaction, by the fruitful steric relief of bulky substrate coordination and transmetalation via a fleeting Pd–N jumping to Pd-π fashion. DFT calculation reveals an interesting Pd-arene-walking characteristic across the carbazolyl plane for attaining a lower energy-preferred route in a catalytic cycle. The theoretical study successfully predicts the stereooutcome and matches the enantioselectivity with the experimental results.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacs.2c06240.

    • Discussions of experimental procedures, characterization details, computational data, 1H, 13C, 19F, and 31P NMR spectra and characterization data of products, and X-ray crystallographic data of [Pd-((S)-L1)Cl2]2, (R)-L2, (R)-L6, L11, (S)-3aa, (S,S)-3ha, and (S)-3ad (PDF)

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    CCDC 2118677, 2118680, 21186822118683, and 21650372165039 contain 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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    Cited By

    This article is cited by 16 publications.

    1. Yuan Sun, Lingzhi Sun, Shaoting Zhang, Zunting Zhang, Tao Wang. Synthesis of C–N Axially Chiral N-Arylbenzo[g]indoles via a Central-to-Axial Chirality Conversion Strategy. Organic Letters 2024, 26 (22) , 4773-4778. https://doi.org/10.1021/acs.orglett.4c01576
    2. Raphael S. Kim, Lebogang O. Kgoadi, Jacob C. Hayes, Derek P. Rainboth, Catherine M. Mudd, Glenn P. A. Yap, Donald A. Watson. Nickel-Catalyzed Atroposelective Cross-Electrophile Coupling of Aryl Halides: A General and Practical Route to Diverse MOP-Type Ligands. Journal of the American Chemical Society 2024, Article ASAP.
    3. Yiming Yang, Changhui Wu, Junhao Xing, Xiaowei Dou. Developing Biarylhemiboronic Esters for Biaryl Atropisomer Synthesis via Dynamic Kinetic Atroposelective Suzuki–Miyaura Cross-Coupling. Journal of the American Chemical Society 2024, 146 (9) , 6283-6293. https://doi.org/10.1021/jacs.3c14450
    4. Xiao-Xiao Hou, Donghui Wei. Mechanism and Origin of Stereoselectivity for the NHC-Catalyzed Desymmetrization Reaction for the Synthesis of Axially Chiral Biaryl Aldehydes. The Journal of Organic Chemistry 2024, 89 (5) , 3133-3142. https://doi.org/10.1021/acs.joc.3c02575
    5. Ryohei Kasahara, Tatsuya Toyoda, Sota Fukasawa, Aoi Takeuchi, Azusa Sato, Akiko Hori, Osamu Kitagawa. Chirality Transfer Intramolecular Pauson–Khand Reaction with N–C Axially Chiral Sulfonamides Bearing an Ene–Yne Structure. Organic Letters 2023, 25 (40) , 7390-7394. https://doi.org/10.1021/acs.orglett.3c02893
    6. Ming Wu, Yi-Wei Chen, Qian Lu, Yong-Bin Wang, Jun Kee Cheng, Peiyuan Yu, Bin Tan. Organocatalytic Si–CAryl Bond Functionalization-Enabled Atroposelective Synthesis of Axially Chiral Biaryl Siloxanes. Journal of the American Chemical Society 2023, 145 (37) , 20646-20654. https://doi.org/10.1021/jacs.3c07839
    7. Mia Guo, Yu Zhang, Meng-Jiao Zhang, Tian Li, Jia-Yi Wu, Feng-Shou Liu. Heteroaryl–Heteroaryl Suzuki–Miyaura Cross-Coupling Enabled by Large-but-Flexible Dibenzobarrelene-Derived Pd-NHC Precatalysts. Organometallics 2023, 42 (15) , 2028-2037. https://doi.org/10.1021/acs.organomet.3c00225
    8. Si-Chen Zhang, Shengping Liu, Xia Wang, Shao-Jie Wang, Hui Yang, Lin Li, Binmiao Yang, Ming Wah Wong, Yu Zhao, Shenci Lu. Enantioselective Access to Triaryl-2-pyrones with Monoaxial or Contiguous C–C Diaxes via Oxidative NHC Catalysis. ACS Catalysis 2023, 13 (4) , 2565-2575. https://doi.org/10.1021/acscatal.2c05570
    9. Man Ho Tse, Pui Ying Choy, Fuk Yee Kwong. Facile Assembly of Modular-Type Phosphines for Tackling Modern Arylation Processes. Accounts of Chemical Research 2022, 55 (24) , 3688-3705. https://doi.org/10.1021/acs.accounts.2c00587
    10. Javid Rzayev, Zhuan Zhang, Natacha Durand, Jean-François Soulé. Upgrading Carbazolyl-Derived Phosphine Ligands Using RhI-Catalyzed PIII-Directed C–H Bond Alkylation for Catalytic CO2-Fixation Reactions. Organic Letters 2022, 24 (37) , 6755-6760. https://doi.org/10.1021/acs.orglett.2c02514
    11. Ivan Keng Wee On, Wenyang Hong, Ye Zhu. Crossing the ortho-hurdle: Ionic stereocontrol enables atroposelective Suzuki-Miyaura coupling. Chem Catalysis 2023, 3 (3) , 100523. https://doi.org/10.1016/j.checat.2023.100523
    12. Katarzyna Kapłon, Sławomir Frynas, Barbara Mirosław, Janusz Lipkowski, Oleg M. Demchuk. An Efficient Asymmetric Cross-Coupling Reaction in Aqueous Media Mediated by Chiral Chelating Mono Phosphane Atropisomeric Biaryl Ligand. Catalysts 2023, 13 (2) , 353. https://doi.org/10.3390/catal13020353
    13. Weiwei Fang, Meiying Kuai, James H. Clark, Tao Tu. Phosphine ligands featuring C−N chiral axis applicable to tetra-ortho-substituted biaryl synthesis. Chinese Chemical Letters 2023, 34 , 108149. https://doi.org/10.1016/j.cclet.2023.108149
    14. Yong Wang, Jingxue Yan, Yiqing Jiang, Zexuan Wei, Zhenlin Tu, Chao Dong, Tao Lu, Yadong Chen, Jie Feng. Atroposelective Amination of Indoles via Chiral Center Induced Chiral Axis Formation. Molecules 2022, 27 (24) , 9008. https://doi.org/10.3390/molecules27249008
    15. Saima Perveen, Shuai Zhang, Linghua Wang, Peidong Song, Yizhao Ouyang, Jiao Jiao, Xin‐Hua Duan, Pengfei Li. Synthesis of Axially Chiral Biaryls via Enantioselective Ullmann Coupling of ortho ‐Chlorinated Aryl Aldehydes Enabled by a Chiral 2,2′‐Bipyridine Ligand. Angewandte Chemie 2022, 134 (47) https://doi.org/10.1002/ange.202212108
    16. Saima Perveen, Shuai Zhang, Linghua Wang, Peidong Song, Yizhao Ouyang, Jiao Jiao, Xin‐Hua Duan, Pengfei Li. Synthesis of Axially Chiral Biaryls via Enantioselective Ullmann Coupling of ortho ‐Chlorinated Aryl Aldehydes Enabled by a Chiral 2,2′‐Bipyridine Ligand. Angewandte Chemie International Edition 2022, 61 (47) https://doi.org/10.1002/anie.202212108