Inversion of Diaza[5]Helicenes Through an N−N Bond Breaking Pathway

  • Toshifumi Kobayashi
    Faculty of Pharmacy Keio University 1-5-30 Shibakoen Minato-ku Tokyo 105-8512 Japan
  • Fumitaka Ishiwari
    Laboratory for Chemistry and Life Science Institute of Innovative Research Tokyo Institute of Technology 4259 Nagatsuta, Midori-ku Yokohama 226-8503 Japan
  • Takanori Fukushima
    Laboratory for Chemistry and Life Science Institute of Innovative Research Tokyo Institute of Technology 4259 Nagatsuta, Midori-ku Yokohama 226-8503 Japan
  • Yuki Nojima
    Department of Chemistry Graduate School of Science Kitasato University 1-15-1 Kitasato Minami-ku Sagamihara Kanagawa 252-0373 Japan
  • Masashi Hasegawa
    Department of Chemistry Graduate School of Science Kitasato University 1-15-1 Kitasato Minami-ku Sagamihara Kanagawa 252-0373 Japan
  • Yasuhiro Mazaki
    Department of Chemistry Graduate School of Science Kitasato University 1-15-1 Kitasato Minami-ku Sagamihara Kanagawa 252-0373 Japan
  • Kengo Hanaya
    Faculty of Pharmacy Keio University 1-5-30 Shibakoen Minato-ku Tokyo 105-8512 Japan
  • Takeshi Sugai
    Faculty of Pharmacy Keio University 1-5-30 Shibakoen Minato-ku Tokyo 105-8512 Japan
  • Shuhei Higashibayashi
    Faculty of Pharmacy Keio University 1-5-30 Shibakoen Minato-ku Tokyo 105-8512 Japan

書誌事項

公開日
2023-06-23
資源種別
journal article
権利情報
  • http://creativecommons.org/licenses/by-nc-nd/4.0/
DOI
  • 10.1002/chem.202301466
公開者
Wiley

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説明

<jats:title>Abstract</jats:title><jats:p>1,1’,10,10’‐Biphenothiazine and its <jats:italic>S</jats:italic>,<jats:italic>S</jats:italic>,<jats:italic>S</jats:italic>’,<jats:italic>S</jats:italic>’‐tetroxide are diaza[5]helicenes with N−N linkages. Kinetic experiments on racemization together with DFT calculations revealed that they undergo inversion through the N−N bond breaking pathway rather than the general conformational pathway. In these diaza[5]helicenes with this inversion mechanism, the reduction of electronic repulsion in the N−N bond by modification of S to SO<jats:sub>2</jats:sub> at the outer position of the helix led to a significantly higher inversion barrier, 35.3 kcal/mol, compared to [5]helicene. 1,1’,10,10’‐Biphenothiazine <jats:italic>S</jats:italic>,<jats:italic>S</jats:italic>,<jats:italic>S</jats:italic>’,<jats:italic>S</jats:italic>’‐tetroxide was highly resistant to acid‐mediated N−N bond breaking and racemization under acidic conditions.</jats:p>

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