ACS Publications. Most Trusted. Most Cited. Most Read
My Activity
CONTENT TYPES

Figure 1Loading Img

Regioselective Palladium-Catalyzed Heterocyclization–Sonogashira Coupling Cascades from 2-Alkynylbenzamides and Terminal Alkynes: Experimental and DFT Studies

  • Francisco Cruz
    Francisco Cruz
    Departamento de Química Orgánica, Facultad de Química, Universidade de Vigo, CINBIO and IIS Galicia Sur, Campus As Lagoas-Marcosende, 36310 Vigo, Spain
  • Belén Vaz
    Belén Vaz
    Departamento de Química Orgánica, Facultad de Química, Universidade de Vigo, CINBIO and IIS Galicia Sur, Campus As Lagoas-Marcosende, 36310 Vigo, Spain
    More by Belén Vaz
  • Unai Vilar
    Unai Vilar
    Departamento de Química Orgánica II, Facultad de Ciencia y Tecnología, Universidad del País Vasco UPV/EHU, Apartado 644, 48080 Bilbao, Spain
    More by Unai Vilar
  • Aitor Ortega
    Aitor Ortega
    Departamento de Química Orgánica II, Facultad de Ciencia y Tecnología, Universidad del País Vasco UPV/EHU, Apartado 644, 48080 Bilbao, Spain
    More by Aitor Ortega
  • Youssef Madich
    Youssef Madich
    Departamento de Química Orgánica II, Facultad de Ciencia y Tecnología, Universidad del País Vasco UPV/EHU, Apartado 644, 48080 Bilbao, Spain
  • Rosana Álvarez*
    Rosana Álvarez
    Departamento de Química Orgánica, Facultad de Química, Universidade de Vigo, CINBIO and IIS Galicia Sur, Campus As Lagoas-Marcosende, 36310 Vigo, Spain
    *E-mail for R.A.: [email protected]
  • , and 
  • José M. Aurrecoechea*
    José M. Aurrecoechea
    Departamento de Química Orgánica II, Facultad de Ciencia y Tecnología, Universidad del País Vasco UPV/EHU, Apartado 644, 48080 Bilbao, Spain
    *E-mail for J.M.A.: [email protected]
Cite this: Organometallics 2018, 37, 21, 3813–3826
Publication Date (Web):October 1, 2018
https://doi.org/10.1021/acs.organomet.8b00519
Copyright © 2018 American Chemical Society

    Article Views

    1322

    Altmetric

    -

    Citations

    LEARN ABOUT THESE METRICS
    Other access options
    Supporting Info (2)»

    Abstract

    Abstract Image

    A regioselective heterocyclization–Sonogashira coupling cascade between 2-alkynylbenzamides and terminal alkynes is described. The reaction proceeds under Pd(II) catalysis, with air used as a terminal oxidant to regenerate the catalyst from the Pd(0) produced in the C–C coupling. The cascade process provides alkynyl-substituted isobenzofuranimine products in a single operation. These products are the result of a 5-exo O-cyclization, while products derived from the alternative 6-endo cyclization mode are observed in minor amounts. Two competing mechanisms have been considered to account for the observed results. Both involve heterocyclization, alkyne C–H activation, and reductive elimination steps but differ in the relative order of the first two. Control experiments using a preformed alkynylpalladium complex have shown that a mechanism starting with alkyne C–H activation is viable. On the other hand, DFT calculations indicate that the alternative cyclization-first mechanism is also competitive, particularly when PPh3 is used as ligand. Calculations also suggest that the exo cyclization is favored over the endo mode by the presence of PPh3 and σ-C Pd ligands in the activated complex undergoing cyclization.

    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. You can change your affiliated institution below.

    Supporting Information

    ARTICLE SECTIONS
    Jump To

    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.organomet.8b00519.

    • Additional experimental details, crystallographic data, energies of calculated structures, NBO data, and NMR spectra (PDF)

    • Cartesian coordinates for all computed structures (XYZ)

    Accession Codes

    CCDC 1555989 and 1560911 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.

    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

    This article is cited by 11 publications.

    1. Belén Vaz, Claudio Martínez, Francisco Cruz, J. Gabriel Denis, Ángel R. de Lera, José M. Aurrecoechea, Rosana Álvarez. Palladium-Catalyzed Aminocyclization–Coupling Cascades: Preparation of Dehydrotryptophan Derivatives and Computational Study. The Journal of Organic Chemistry 2021, 86 (13) , 8766-8785. https://doi.org/10.1021/acs.joc.1c00636
    2. Yiying Yang, Yanhong Liu, Rongxiu Zhu, Chengbu Liu, Dongju Zhang. Theoretical Insight into the Mechanism and Origin of Divergent Reactivity in the Synthesis of Benzo-Heterocycles from o-Alkynylbenzamides Catalyzed by Gold and Platinum Complexes. The Journal of Organic Chemistry 2019, 84 (15) , 9705-9713. https://doi.org/10.1021/acs.joc.9b01441
    3. Pui Ying Choy, Kin Boon Gan, Fuk Yee Kwong. Recent Expedition in Pd‐Catalyzed Sonogashira Coupling and Related Processes †. Chinese Journal of Chemistry 2023, 41 (9) , 1099-1118. https://doi.org/10.1002/cjoc.202200703
    4. Alejandro Lumbreras‐Teijeiro, Matea Bacic, Judit Oliver‐Meseguer, Antonio Leyva‐Pérez. A Cascade Sonogashira Cross‐Coupling‐Substitution‐Elimination Reaction for the Synthesis of Linear Conjugated Dienynes. Chemistry – A European Journal 2022, 28 (71) https://doi.org/10.1002/chem.202202421
    5. Zhide Zhang, Yangling Deng, Ming Hou, Xiaojing Lai, Meng Guan, Fengzhi Zhang, Rui Qi, Guanyinsheng Qiu. Iron/photoredox dual catalysis for acyl nitrene-based C–O bond formation towards phthalides. Chemical Communications 2022, 58 (98) , 13644-13647. https://doi.org/10.1039/D2CC04917A
    6. J. C. Gonzalez‐Gomez, F. Alonso. Transition‐Metal Catalyzed Reactions. 2021, 513-551. https://doi.org/10.1002/9781119531975.ch13
    7. Yu‐Ping He, Jian Cao, Hua Wu, Qian Wang, Jieping Zhu. Catalytic Enantioselective Aminopalladation–Heck Cascade. Angewandte Chemie 2021, 133 (13) , 7169-7173. https://doi.org/10.1002/ange.202016001
    8. Yu‐Ping He, Jian Cao, Hua Wu, Qian Wang, Jieping Zhu. Catalytic Enantioselective Aminopalladation–Heck Cascade. Angewandte Chemie International Edition 2021, 60 (13) , 7093-7097. https://doi.org/10.1002/anie.202016001
    9. Jianxiao Li, Shaorong Yang, Wanqing Wu, Huanfeng Jiang. Palladium‐Catalyzed Cascade Cyclization/Alkynylation Reactions. Chemistry – An Asian Journal 2019, 14 (23) , 4114-4128. https://doi.org/10.1002/asia.201901202
    10. Jing Zhang, Jing-Ning Lv, Fengyue Zhao, Jiaying Sun. Computational study on the catalyst-controlled synthesis of C2-substituted quinolines through the annulation of 2-vinylanilines and alkynoates. Journal of Organometallic Chemistry 2019, 897 , 7-12. https://doi.org/10.1016/j.jorganchem.2019.06.021
    11. Jianxiao Li, Ruikang Huang, Can Li, Shao Lin, Wanqing Wu, Huanfeng Jiang. Assembly of Functionalized 4‐Alkynylisoxazoles by Palladium‐Catalyzed Three‐Component Cascade Cyclization/Alkynylation. Chemistry – An Asian Journal 2019, 14 (13) , 2309-2315. https://doi.org/10.1002/asia.201900476

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    You’ve supercharged your research process with ACS and Mendeley!

    STEP 1:
    Click to create an ACS ID

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    MENDELEY PAIRING EXPIRED
    Your Mendeley pairing has expired. Please reconnect