An Atropisomerism Study of Large Cycloarylenes: [<i>n</i>]Cyclo‐4,10‐Pyrenylenes’ Case

  • Ryo Kurosaki
    Division of Materials Science Graduate School of Science and Technology Nara Institute of Science and Technology (NAIST) 8916-5 Takayama-cho Ikoma 630-0192 Japan
  • Hirofumi Morimoto
    Division of Materials Science Graduate School of Science and Technology Nara Institute of Science and Technology (NAIST) 8916-5 Takayama-cho Ikoma 630-0192 Japan
  • Kyohei Matsuo
    Division of Materials Science Graduate School of Science and Technology Nara Institute of Science and Technology (NAIST) 8916-5 Takayama-cho Ikoma 630-0192 Japan
  • Hironobu Hayashi
    Division of Materials Science Graduate School of Science and Technology Nara Institute of Science and Technology (NAIST) 8916-5 Takayama-cho Ikoma 630-0192 Japan
  • Hiroko Yamada
    Division of Materials Science Graduate School of Science and Technology Nara Institute of Science and Technology (NAIST) 8916-5 Takayama-cho Ikoma 630-0192 Japan
  • Naoki Aratani
    Division of Materials Science Graduate School of Science and Technology Nara Institute of Science and Technology (NAIST) 8916-5 Takayama-cho Ikoma 630-0192 Japan

抄録

<jats:title>Abstract</jats:title><jats:p>An atropisomerism of large cycloarylenes was studied using [<jats:italic>n</jats:italic>]cyclo‐4,10‐pyrenylenes (<jats:italic>n</jats:italic>=6–21) as an illustrative example with two simple assumptions: (1) alternating configurations (<jats:italic>R</jats:italic>,<jats:italic>S</jats:italic>,<jats:italic>R</jats:italic>,<jats:italic>S</jats:italic>,…) are thermodynamically most stable, and (2) three consecutive identical configurations (<jats:italic>R</jats:italic>,<jats:italic>R</jats:italic>,<jats:italic>R</jats:italic>or<jats:italic>S</jats:italic>,<jats:italic>S</jats:italic>,<jats:italic>S</jats:italic>) are prevented. Ni‐mediated coupling of a 5,9‐diiodopyrene gave a series of directly‐linked cyclic pyrene oligomers in one‐pot reaction. As‐synthesized cyclic hexamer was assigned as an (<jats:italic>R</jats:italic>,<jats:italic>S</jats:italic>,<jats:italic>S</jats:italic>,<jats:italic>R</jats:italic>,<jats:italic>R</jats:italic>,<jats:italic>S</jats:italic>) structure, converted into an (<jats:italic>R</jats:italic>,<jats:italic>S</jats:italic>,<jats:italic>R</jats:italic>,<jats:italic>S</jats:italic>,<jats:italic>R</jats:italic>,<jats:italic>S</jats:italic>)‐form upon heating. Cyclic heptamer consists of two types of<jats:italic>C</jats:italic><jats:sub>2</jats:sub>symmetric structures predicted from assumption (2), one of which was convergent to one another by heating. Three atropisomers of cyclic octamer were analyzed from the possible five candidates by means of<jats:sup>1</jats:sup>H nuclear magnetic resonance (NMR) spectroscopy, and the conversion process to (<jats:italic>R</jats:italic>,<jats:italic>S</jats:italic>,<jats:italic>R</jats:italic>,<jats:italic>S</jats:italic>,<jats:italic>R</jats:italic>,<jats:italic>S</jats:italic>,<jats:italic>R</jats:italic>,<jats:italic>S</jats:italic>) configurations upon heating was investigated. In total, according to two simple rules, the analysis of atropisomerism could be performed smoothly.</jats:p>

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