Construction of Condensed Polycyclic Aromatic Frameworks through Intramolecular Cycloaddition Reactions Involving Arynes Bearing an Internal Alkyne Moiety

  • Suguru Yoshida
    Laboratory of Chemical Bioscience, Institute of Biomaterials and Bioengineering Tokyo Medical and Dental University (TMDU) 2-3-10 Kanda-Surugadai, Chiyoda-ku Tokyo 101-0062 Japan
  • Keita Shimizu
    Laboratory of Chemical Bioscience, Institute of Biomaterials and Bioengineering Tokyo Medical and Dental University (TMDU) 2-3-10 Kanda-Surugadai, Chiyoda-ku Tokyo 101-0062 Japan
  • Keisuke Uchida
    Laboratory of Chemical Bioscience, Institute of Biomaterials and Bioengineering Tokyo Medical and Dental University (TMDU) 2-3-10 Kanda-Surugadai, Chiyoda-ku Tokyo 101-0062 Japan
  • Yuki Hazama
    Laboratory of Chemical Bioscience, Institute of Biomaterials and Bioengineering Tokyo Medical and Dental University (TMDU) 2-3-10 Kanda-Surugadai, Chiyoda-ku Tokyo 101-0062 Japan
  • Kazunobu Igawa
    Institute for Materials Chemistry and Engineering Kyushu University 6-1 Kasuga-koen, Kasuga Fukuoka 816-8580 Japan
  • Katsuhiko Tomooka
    Institute for Materials Chemistry and Engineering Kyushu University 6-1 Kasuga-koen, Kasuga Fukuoka 816-8580 Japan
  • Takamitsu Hosoya
    Laboratory of Chemical Bioscience, Institute of Biomaterials and Bioengineering Tokyo Medical and Dental University (TMDU) 2-3-10 Kanda-Surugadai, Chiyoda-ku Tokyo 101-0062 Japan

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<jats:title>Abstract</jats:title><jats:p>Facile synthetic methods for condensed polycyclic aromatic compounds via aryne intermediates are reported. The generation of arynes bearing a (3‐arylpropargyl)oxy group from the corresponding <jats:italic>o</jats:italic>‐iodoaryl triflate‐type precursors efficiently afforded arene‐fused oxaacenaphthene derivatives, which were formed through intramolecular [2+4] cycloaddition. Extending the method to the generation of arynes bearing a 1,3‐diyne moiety led to a continuous generation of naphthalyne intermediate through the hexadehydro Diels–Alder reaction involving the aryne triple bond. This novel type of aryne‐relay chemistry enabled the synthesis of a unique aminoarylated oxaacenaphthene derivative and highly ring‐fused anthracene derivatives.</jats:p>

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