ACS Publications. Most Trusted. Most Cited. Most Read
Spatial Anion Control on Palladium for Mild C–H Arylation of Arenes
My Activity

Figure 1Loading Img
    Communication

    Spatial Anion Control on Palladium for Mild C–H Arylation of Arenes
    Click to copy article linkArticle link copied!

    Other Access OptionsSupporting Information (2)

    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2020, 142, 45, 19040–19046
    Click to copy citationCitation copied!
    https://doi.org/10.1021/jacs.0c09611
    Published October 30, 2020
    Copyright © 2020 American Chemical Society

    Abstract

    Click to copy section linkSection link copied!
    Abstract Image

    C–H arylation of arenes without the use of directing groups is a challenge, even for simple molecules, such as benzene. We describe spatial anion control as a concept for the design of catalytic sites for C–H bond activation, thereby enabling nondirected C–H arylation of arenes at ambient temperature. The mild conditions enable late-stage structural diversification of biologically relevant small molecules, and site-selectivity complementary to that obtained with other methods of arene functionalization can be achieved. These results reveal the potential of spatial anion control in transition-metal catalysis for the functionalization of C–H bonds under mild conditions.

    Copyright © 2020 American Chemical Society

    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 at https://pubs.acs.org/doi/10.1021/jacs.0c09611.

    • Experimental details, characterization spectra, single-crystal data, and computational details (PDF)

    • Crystallographic data (CIF)

    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

    This article is cited by 30 publications.

    1. Kang Fu, Lei Shi. Enabling Site-Selective C–H Functionalization of Aliphatic Alcohols and Amines with exo-Directing Groups by Tether-Tunable Design of PdII/PdIV Catalysis. ACS Catalysis 2024, 14 (22) , 17077-17083. https://doi.org/10.1021/acscatal.4c05553
    2. Meng-Ying Sun, Sheung Chit Cheung, Xue-Zhi Wang, Ji-Kang Jin, Jun Guo, Dan Li, Jian He. Structural Reassignment of Covalent Organic Framework-Supported Palladium Species: Heterogenized Palladacycles as Efficient Catalysts for Sustainable C–H Activation. ACS Central Science 2024, 10 (10) , 1848-1860. https://doi.org/10.1021/acscentsci.4c00660
    3. Guangrong Meng, Jie-Lun Yan, Nikita Chekshin, Daniel A. Strassfeld, Jin-Quan Yu. Ligand-Controlled Nondirected meta- or para-C–H Olefination of Silyl-Protected Phenols. ACS Catalysis 2024, 14 (17) , 12806-12813. https://doi.org/10.1021/acscatal.4c03858
    4. Min Liu, Baojie Qiu, Zhuo Zhang, Yulong Zheng, Junyu Yuan, Hailing Li, Xingxian Zhang. Ligand-Enabled C6-Selective C–H Arylation of Pyrrolo[2,3-d] Pyrimidine Derivatives with Pd Catalysts: An Approach to the Synthesis of EGFR Inhibitor AEE-788. The Journal of Organic Chemistry 2024, 89 (11) , 8023-8034. https://doi.org/10.1021/acs.joc.4c00667
    5. Sandip Porey, Yogesh Bairagi, Srimanta Guin, Xinglong Zhang, Debabrata Maiti. Nondirected C–H/C–F Coupling for the Synthesis of α-Fluoro Olefinated Arenes. ACS Catalysis 2023, 13 (21) , 14000-14011. https://doi.org/10.1021/acscatal.3c02975
    6. Simon Kaltenberger, Manuel van Gemmeren. Controlling Reactivity and Selectivity in the Nondirected C–H Activation of Arenes with Palladium. Accounts of Chemical Research 2023, 56 (18) , 2459-2472. https://doi.org/10.1021/acs.accounts.3c00354
    7. Mirxan Farizyan, Arup Mondal, Sourjya Mal, Fritz Deufel, Manuel van Gemmeren. Palladium-Catalyzed Nondirected Late-Stage C–H Deuteration of Arenes. Journal of the American Chemical Society 2021, 143 (40) , 16370-16376. https://doi.org/10.1021/jacs.1c08233
    8. Dian Wang, Chase A. Salazar, Shannon S. Stahl. Catalyst-Controlled Regioselectivity in Pd-Catalyzed Aerobic Oxidative Arylation of Indoles. Organometallics 2021, 40 (14) , 2198-2203. https://doi.org/10.1021/acs.organomet.1c00139
    9. Tommaso Ruggiero, Kristof Van Hecke, Catherine S. J. Cazin, Steven P. Nolan. [Cu(NHC)(OR)] (R = C(CF 3 ) 3 ) complexes for N–H and S–H bond activation and as pre-catalysts in the Chan–Evans–Lam reaction. Dalton Transactions 2025, 54 (4) , 1329-1333. https://doi.org/10.1039/D4DT03322A
    10. Cintya Pinilla, Mario García-Zarza, Ana C. Albéniz. Metal–ligand cooperation and synergistic palladium catalysis for the dual ligand system [2,2′-bipyridin]-6(1 H )–one/PCy 3 : milder conditions for the undirected C–H arylation of arenes. Organic Chemistry Frontiers 2025, 12 (2) , 467-477. https://doi.org/10.1039/D4QO01877J
    11. Elisa González‐Fernández, Nittert Marinus, Jyoti Dhankhar, Anthony Linden, Ilija Čorić. Control over Anion Coordination on Pd(II), Cu(I), and Ag(I) with Regioisomeric Phosphine‐Carboxylate Ligands. Chemistry – A European Journal 2024, 30 (37) https://doi.org/10.1002/chem.202401215
    12. Da Li, Yuji Wang, Shiyu Wang, Shunxi Dong. The Effect of Basic Ligands and Alkenes on the Regioselectivity of C−H Additions of Tertiary Amines to Alkenes. Chemistry – A European Journal 2024, 30 (32) https://doi.org/10.1002/chem.202401014
    13. Ke‐Zuan Deng, Verena Sukowski, M. Ángeles Fernández‐Ibáñez. Non‐Directed C−H Arylation of Anisole Derivatives via Pd/S,O‐Ligand Catalysis. Angewandte Chemie 2024, 136 (19) https://doi.org/10.1002/ange.202400689
    14. Ke‐Zuan Deng, Verena Sukowski, M. Ángeles Fernández‐Ibáñez. Non‐Directed C−H Arylation of Anisole Derivatives via Pd/S,O‐Ligand Catalysis. Angewandte Chemie International Edition 2024, 63 (19) https://doi.org/10.1002/anie.202400689
    15. Jun Pu, Lei Chen, Rui-Rui Wu, Peng Ye, Huan-Le Li, Shuang Wang, Zhen-Yuan Xu, Shao-Jie Lou, Dan-Qian Xu. Non-directed Pd-catalysed C–H arylation of [2.2]paracyclophane. Chemical Communications 2023, 59 (61) , 9348-9351. https://doi.org/10.1039/D3CC02546B
    16. Weidong Shang, Hongbao Sun, Wei Chen, Jie Liu. Diversification of pharmaceutical molecules via late-stage C(sp2)–H functionalization. Green Synthesis and Catalysis 2023, 4 (2) , 104-123. https://doi.org/10.1016/j.gresc.2022.12.007
    17. Neha Kumari, Ruchika Sharma, Archana Akaram Yadav, Sandeep Ashok Sankpal, Jayakumar Mohan Raj, Saminathan Murugavel, Rajni Kant. Synthesis, crystal structure, DFT/HF, Hirshfeld surface, and molecular docking analysis of 4-(tert-butyl)-4-nitro-1,1-biphenyl. European Journal of Chemistry 2023, 14 (1) , 90-98. https://doi.org/10.5155/eurjchem.14.1.90-98.2386
    18. Kananat Naksomboon, Enrique Gómez-Bengoa, Jaya Mehara, Jana Roithová, Edwin Otten, M. Ángeles Fernández-Ibáñez. Mechanistic studies of the palladium-catalyzed S,O-ligand promoted C–H olefination of aromatic compounds. Chemical Science 2023, 14 (11) , 2943-2953. https://doi.org/10.1039/D2SC06840K
    19. Preeti Yadav, Nivedha Velmurugan, Christine K. Luscombe. Recent Advances in Room-Temperature Direct C–H Arylation Methodologies. Synthesis 2023, 55 (01) , 1-26. https://doi.org/10.1055/a-1939-7052
    20. Arup Mondal, Manuel van Gemmeren. Silberfreie C−H‐Aktivierung: Strategische Ansätze zur Erschließung des vollen Potenzials von C−H‐Aktivierungen in der nachhaltigen organischen Synthese. Angewandte Chemie 2022, 134 (48) https://doi.org/10.1002/ange.202210825
    21. Arup Mondal, Manuel van Gemmeren. Silver‐Free C−H Activation: Strategic Approaches towards Realizing the Full Potential of C−H Activation in Sustainable Organic Synthesis. Angewandte Chemie International Edition 2022, 61 (48) https://doi.org/10.1002/anie.202210825
    22. Jyoti Dhankhar, Micha D. Hofer, Anthony Linden, Ilija Čorić. Site‐Selective C−H Arylation of Diverse Arenes Ortho to Small Alkyl Groups. Angewandte Chemie 2022, 134 (39) https://doi.org/10.1002/ange.202205470
    23. Jyoti Dhankhar, Micha D. Hofer, Anthony Linden, Ilija Čorić. Site‐Selective C−H Arylation of Diverse Arenes Ortho to Small Alkyl Groups. Angewandte Chemie International Edition 2022, 61 (39) https://doi.org/10.1002/anie.202205470
    24. Verena Sukowski, Manuela van Borselen, Simon Mathew, M. Ángeles Fernández‐Ibáñez. S,O‐Ligand Promoted meta ‐C−H Arylation of Anisole Derivatives via Palladium/Norbornene Catalysis. Angewandte Chemie 2022, 134 (31) https://doi.org/10.1002/ange.202201750
    25. Verena Sukowski, Manuela van Borselen, Simon Mathew, M. Ángeles Fernández‐Ibáñez. S,O‐Ligand Promoted meta ‐C−H Arylation of Anisole Derivatives via Palladium/Norbornene Catalysis. Angewandte Chemie International Edition 2022, 61 (31) https://doi.org/10.1002/anie.202201750
    26. Jyoti Dhankhar, Ilija Čorić. Introduction to Spatial Anion Control for Direct C–H Arylation. Synlett 2022, 33 (06) , 503-512. https://doi.org/10.1055/s-0040-1719860
    27. Yuki Kanai, Dorian Müller‐Borges, Herbert Plenio. The Regioselective Arylation of 1,3‐Benzodioxoles. Advanced Synthesis & Catalysis 2022, 364 (3) , 679-688. https://doi.org/10.1002/adsc.202101014
    28. Qian Shang, Haifang Tang, Yongping Liu, MingMing Yin, Lebin Su, Shimin Xie, Lixin Liu, Wen Yang, Yi Chen, Jianyu Dong, Yongbo Zhou, Shuang-Feng Yin. Cu( i ) catalysis for selective condensation/bicycloaromatization of two different arylalkynes: direct and general construction of functionalized C–N axial biaryl compounds. Chemical Science 2021, 13 (1) , 263-273. https://doi.org/10.1039/D1SC03865F
    29. Philipp Wedi, Mirxan Farizyan, Klaus Bergander, Christian Mück‐Lichtenfeld, Manuel van Gemmeren. Mechanismus der Aren‐limitierten, nicht‐dirigierten C‐H‐Aktivierung von Arenen mit Palladium**. Angewandte Chemie 2021, 133 (28) , 15770-15779. https://doi.org/10.1002/ange.202105092
    30. Philipp Wedi, Mirxan Farizyan, Klaus Bergander, Christian Mück‐Lichtenfeld, Manuel van Gemmeren. Mechanism of the Arene‐Limited Nondirected C−H Activation of Arenes with Palladium**. Angewandte Chemie International Edition 2021, 60 (28) , 15641-15649. https://doi.org/10.1002/anie.202105092

    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2020, 142, 45, 19040–19046
    Click to copy citationCitation copied!
    https://doi.org/10.1021/jacs.0c09611
    Published October 30, 2020
    Copyright © 2020 American Chemical Society

    Article Views

    12k

    Altmetric

    -

    Citations

    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.