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Synthesis of Aza[n]helicenes (n = 4–7) via Photocyclodehydrochlorination of 1-Chloro-N-aryl-2-naphthamides
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    Synthesis of Aza[n]helicenes (n = 4–7) via Photocyclodehydrochlorination of 1-Chloro-N-aryl-2-naphthamides
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    • Lubomír Váňa
      Lubomír Váňa
      Department of Advanced Materials and Organic Synthesis, Institute of Chemical Process Fundamentals of the Czech Academy of Sciences, v. v. i., Rozvojová 135, 165 02 Prague 6, Czech Republic
    • Martin Jakubec
      Martin Jakubec
      Department of Advanced Materials and Organic Synthesis, Institute of Chemical Process Fundamentals of the Czech Academy of Sciences, v. v. i., Rozvojová 135, 165 02 Prague 6, Czech Republic
    • Jan Sýkora*
      Jan Sýkora
      Department of Analytical Chemistry, Institute of Chemical Process Fundamentals of the Czech Academy of Sciences, v. v. i., Rozvojová 135, 165 02 Prague 6, Czech Republic
      *E-mail: [email protected]
      More by Jan Sýkora
    • Ivana Císařová
      Ivana Císařová
      Department of Inorganic Chemistry, Faculty of Science, Charles University in Prague, Hlavova 2030, 128 40 Prague 2, Czech Republic
    • Jaroslav Žádný
      Jaroslav Žádný
      Department of Advanced Materials and Organic Synthesis, Institute of Chemical Process Fundamentals of the Czech Academy of Sciences, v. v. i., Rozvojová 135, 165 02 Prague 6, Czech Republic
    • Jan Storch
      Jan Storch
      Department of Advanced Materials and Organic Synthesis, Institute of Chemical Process Fundamentals of the Czech Academy of Sciences, v. v. i., Rozvojová 135, 165 02 Prague 6, Czech Republic
      More by Jan Storch
    • Vladimír Církva*
      Vladimír Církva
      Department of Advanced Materials and Organic Synthesis, Institute of Chemical Process Fundamentals of the Czech Academy of Sciences, v. v. i., Rozvojová 135, 165 02 Prague 6, Czech Republic
      *E-mail: [email protected]
    Other Access OptionsSupporting Information (2)

    The Journal of Organic Chemistry

    Cite this: J. Org. Chem. 2022, 87, 11, 7150–7166
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    https://doi.org/10.1021/acs.joc.2c00375
    Published May 12, 2022
    Copyright © 2022 American Chemical Society

    Abstract

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    A series of aza[n]helicenes (n = 4–7) was synthesized using a photocyclodehydrochlorination of 1-chloro-N-aryl-2-naphthamides as a general synthetic procedure introducing the nitrogen atom to the third ring of the helicene framework. The effect of the nitrogen presence in the helicene skeleton on the physicochemical properties of the prepared aza[n]helicenes was studied and compared to those of the parent carbo-analogues. The insertion of a nitrogen atom into the outer edge of the helicene molecule has a severe impact on certain physicochemical properties such as optical rotation, electrostatic potentials, and intermolecular interactions. On the other hand, some other properties such as UV/vis, fluorescence, and phosphorescence spectra remained almost unaffected when compared to the parent carbohelicenes. A nitrogen atom can be also used for further derivatization, which can lead to further modification of helicene properties, as manifested here in the fluorescence changes induced by protonation.

    Copyright © 2022 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.joc.2c00375.

    • FAIR data, including the primary NMR FID files, for compounds 2ac, 5, 6, 810, 11ad, 12ad, 13ac, 14, 15ad, and 16 (ZIP)

    • Photochemical reactor setup; UV–vis, fluorescence, and phosphorescence spectra; X-ray crystallography details; separation of enantiomers and racemization barrier determination; and DFT calculation details (PDF)

    Accession Codes

    CCDC 21524612152462 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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    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!

    This article is cited by 7 publications.

    1. Martin Kos, Tomáš Beránek, Ivana Císařová, Petra Cuřínová, Jaroslav Žádný, Jan Storch, Vladimír Církva, Martin Jakubec. Resolution of 9,10-Diketo[7]helicene and Its Use in One-Step Preparation of Helicene-Based D–A–D Push–Pull Systems. The Journal of Organic Chemistry 2024, 89 (11) , 7495-7502. https://doi.org/10.1021/acs.joc.4c00135
    2. Giuseppina Raffaini. Adsorption and Self-Aggregation of Chiral [5]-Aza[6]helicenes on DNA Architecture: A Molecular Dynamics Study. The Journal of Physical Chemistry B 2023, 127 (39) , 8285-8295. https://doi.org/10.1021/acs.jpcb.3c02487
    3. Yuexia Dong, Zhen Sun, Wan Xu, Zhiying Ma, Shuai Qiu, Chunli Li, Hua Wang. Construction and Phosphorescence Behavior of S/Se-Heteroaromatics/Phenanthrene-Fused Hetero[9]helicenes. Organic Letters 2023, 25 (36) , 6715-6719. https://doi.org/10.1021/acs.orglett.3c02567
    4. Yong-Ze Chen, Ting-Hui Ding, Qiang-Qiang Li, Jian-Ping Qu, Yan-Biao Kang. Ambient Temperature Dehydrogenative C(Ar)–H Carbonylative Lactamization of 2-Arylanilines Using DMF as C1-Source. Organic Letters 2023, 25 (15) , 2611-2615. https://doi.org/10.1021/acs.orglett.3c00585
    5. Tomáš Beránek, Martin Kos, Lubomír Váňa, Ivana Císařová, Jan Sýkora, Jan Storch, Vladimír Církva, Martin Jakubec. Modification of optical properties in helicenes via construction of phosphine oxide-based push-pull systems. Dyes and Pigments 2023, 210 , 111039. https://doi.org/10.1016/j.dyepig.2022.111039
    6. Pushpendra Mani Shukla, Aditya Bhattacharya, Aniruddh Pratap, Akash Pradhan, Puspita Sinha, Tanishk Soni, Biswajit Maji. HFIP-promoted halo-carbocyclizations of N - and O -tethered arene–alkene substrates to access all halo (X = Br, I, Cl)-functionalized tetrahydroquinoline and chroman cores. Organic & Biomolecular Chemistry 2022, 20 (41) , 8136-8144. https://doi.org/10.1039/D2OB01597H
    7. . 7-Azahelicene Syntheses via Photocyclodehydrochlorination. Synfacts 2022, 0974. https://doi.org/10.1055/s-0042-1752937

    The Journal of Organic Chemistry

    Cite this: J. Org. Chem. 2022, 87, 11, 7150–7166
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.joc.2c00375
    Published May 12, 2022
    Copyright © 2022 American Chemical Society

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