Anti‐Aromatic versus Induced Paratropicity: Synthesis and Interrogation of a Dihydro‐diazatrioxa[9]circulene with a Proton Placed Directly above the Central Ring

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  • Stephan K. Pedersen
    University of Copenhagen Department of Chemistry Universitetsparken 5 2100 Copenhagen Ø Denmark
  • Kristina Eriksen
    University of Copenhagen Department of Chemistry Universitetsparken 5 2100 Copenhagen Ø Denmark
  • Nataliya N. Karaush‐Karmazin
    Department of Chemistry and Nanomaterials Science Bohdan Khmelnytsky National University 18031 Cherkasy Ukraine
  • Boris Minaev
    Department of Chemistry and Nanomaterials Science Bohdan Khmelnytsky National University 18031 Cherkasy Ukraine
  • Hans Ågren
    Division of Theoretical Chemistry and Biology School of Engineering Sciences in Chemistry, Biotechnology and Health KTH Royal Institute of Technology 10691 Stockholm Sweden
  • Gleb V. Baryshnikov
    Division of Theoretical Chemistry and Biology School of Engineering Sciences in Chemistry, Biotechnology and Health KTH Royal Institute of Technology 10691 Stockholm Sweden
  • Michael Pittelkow
    University of Copenhagen Department of Chemistry Universitetsparken 5 2100 Copenhagen Ø Denmark

書誌事項

公開日
2020-02-20
権利情報
  • http://onlinelibrary.wiley.com/termsAndConditions#vor
DOI
  • 10.1002/anie.201913552
公開者
Wiley

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説明

<jats:title>Abstract</jats:title><jats:p>We present a high‐yielding intramolecular oxidative coupling within a diazadioxa[10]helicene to give a dihydro‐diazatrioxa[9]circulene. This is the first [<jats:italic>n</jats:italic>]circulene containing more than eight <jats:italic>ortho</jats:italic>‐annulated rings (<jats:italic>n</jats:italic>>8). The single‐crystal X‐ray structure reveals a tight columnar packing, with a proton from a pendant naphthalene moiety centred directly above the central nine‐membered ring. This distinct environment induces a significant magnetic deshielding effect on that particular proton as determined by <jats:sup>1</jats:sup>H NMR spectroscopy. The origin of the deshielding effect was investigated computationally in terms of the NICS values. It is established that the deshielding effect originates from an induced paratropic ring current from the seven aromatic rings of the [9]circulene structure, and is not due to the nine‐membered ring being antiaromatic. UV/Vis spectroscopy reveals more efficient conjugation in the prepared diazatrioxa[9]circulene compared to the parent helical azaoxa[10]helicenes, and DFT calculations, including energy levels, confirm the experimental observations.</jats:p>

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