Double‐Stranded Helical Oligomers Covalently Bridged by Rotary Cyclic Boronate Esters

  • Hiroki Iida
    Department of Molecular Design and Engineering Graduate School of Engineering Nagoya University, Chikusa-ku Nagoya 464-8603 Japan
  • Kenji Ohmura
    Department of Molecular Design and Engineering Graduate School of Engineering Nagoya University, Chikusa-ku Nagoya 464-8603 Japan
  • Ryuta Noda
    Department of Molecular Design and Engineering Graduate School of Engineering Nagoya University, Chikusa-ku Nagoya 464-8603 Japan
  • Soichiro Iwahana
    Department of Molecular Design and Engineering Graduate School of Engineering Nagoya University, Chikusa-ku Nagoya 464-8603 Japan
  • Hiroshi Katagiri
    Graduate School of Science and Engineering Yamagata University 4-3-16 Jonan, Yonezawa, Yamagata 992-8510 Japan
  • Naoki Ousaka
    Department of Molecular Design and Engineering Graduate School of Engineering Nagoya University, Chikusa-ku Nagoya 464-8603 Japan
  • Taku Hayashi
    Institute of Transformative Bio-Molecules (WPI-ITbM) and Department of Chemistry Graduate School of Science Nagoya University Nagoya 464-8602 Japan
  • Yuh Hijikata
    Institute of Transformative Bio-Molecules (WPI-ITbM) and Department of Chemistry Graduate School of Science Nagoya University Nagoya 464-8602 Japan
  • Stephan Irle
    Institute of Transformative Bio-Molecules (WPI-ITbM) and Department of Chemistry Graduate School of Science Nagoya University Nagoya 464-8602 Japan
  • Eiji Yashima
    Department of Molecular Design and Engineering Graduate School of Engineering Nagoya University, Chikusa-ku Nagoya 464-8603 Japan

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<jats:title>Abstract</jats:title><jats:p>Novel double helices covalently bridged by cyclic boronate esters were synthesized from complementary dimers with an <jats:italic>m</jats:italic>‐terphenyl backbone joined by a chiral or achiral phenylene linker bearing diethyl boronates and diols, respectively. The X‐ray crystallographic analysis and variable‐temperature NMR and circular dichroism measurements, along with theoretical calculations, revealed that the double helices function as a “molecular rotor” in which the cyclic boronate ester units rotate, yielding two stable rotamers at low temperatures. Moreover, our data indicates that the covalently bonded double helices can undergo a unique helix‐inversion simultaneously with a rotational motion of the boronate esters.</jats:p>

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