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Rapid access to polycyclic N-heteroarenes from unactivated, simple azines via a base-promoted Minisci-type annulation

Author

Listed:
  • Jae Bin Lee

    (Ulsan National Institute of Science and Technology (UNIST))

  • Gun Ha Kim

    (Ulsan National Institute of Science and Technology (UNIST))

  • Ji Hwan Jeon

    (Ulsan National Institute of Science and Technology (UNIST))

  • Seo Yeong Jeong

    (Ulsan National Institute of Science and Technology (UNIST))

  • Soochan Lee

    (Ulsan National Institute of Science and Technology (UNIST))

  • Jaehyun Park

    (School of Energy and Chemical Engineering, UNIST)

  • Doyoung Lee

    (School of Energy and Chemical Engineering, UNIST)

  • Youngkook Kwon

    (School of Energy and Chemical Engineering, UNIST)

  • Jeong Kon Seo

    (UNIST Central Research Facilities (UCRF), UNIST)

  • Joong-Hyun Chun

    (Yonsei University College of Medicine)

  • Seok Ju Kang

    (School of Energy and Chemical Engineering, UNIST)

  • Wonyoung Choe

    (Ulsan National Institute of Science and Technology (UNIST))

  • Jan-Uwe Rohde

    (Ulsan National Institute of Science and Technology (UNIST))

  • Sung You Hong

    (Ulsan National Institute of Science and Technology (UNIST))

Abstract

Conventional synthetic methods to yield polycyclic heteroarenes have largely relied on metal-mediated arylation reactions requiring pre-functionalised substrates. However, the functionalisation of unactivated azines has been restricted because of their intrinsic low reactivity. Herein, we report a transition-metal-free, radical relay π-extension approach to produce N-doped polycyclic aromatic compounds directly from simple azines and cyclic iodonium salts. Mechanistic and electron paramagnetic resonance studies provide evidence for the in situ generation of organic electron donors, while chemical trapping and electrochemical experiments implicate an iodanyl radical intermediate serving as a formal biaryl radical equivalent. This intermediate, formed by one-electron reduction of the cyclic iodonium salt, acts as the key intermediate driving the Minisci-type arylation reaction. The synthetic utility of this radical-based annulative π-extension method is highlighted by the preparation of an N-doped heptacyclic nanographene fragment through fourfold C–H arylation.

Suggested Citation

  • Jae Bin Lee & Gun Ha Kim & Ji Hwan Jeon & Seo Yeong Jeong & Soochan Lee & Jaehyun Park & Doyoung Lee & Youngkook Kwon & Jeong Kon Seo & Joong-Hyun Chun & Seok Ju Kang & Wonyoung Choe & Jan-Uwe Rohde &, 2022. "Rapid access to polycyclic N-heteroarenes from unactivated, simple azines via a base-promoted Minisci-type annulation," Nature Communications, Nature, vol. 13(1), pages 1-9, December.
    • Handle: RePEc:nat:natcom:v:13:y:2022:i:1:d:10.1038_s41467-022-30086-0
    DOI: 10.1038/s41467-022-30086-0
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    References listed on IDEAS

    as
    1. Kyohei Ozaki & Katsuaki Kawasumi & Mari Shibata & Hideto Ito & Kenichiro Itami, 2015. "One-shot K-region-selective annulative π-extension for nanographene synthesis and functionalization," Nature Communications, Nature, vol. 6(1), pages 1-8, May.
    2. Wataru Matsuoka & Hideto Ito & David Sarlah & Kenichiro Itami, 2021. "Diversity-oriented synthesis of nanographenes enabled by dearomative annulative π-extension," Nature Communications, Nature, vol. 12(1), pages 1-9, December.
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