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<p>The synthesis of specific multicyclic chiral macrocycles from other multiple possible isomers and constructing communication systems among their chiral cyclic units remain challenging. We herein report a series of hexacyclic chiral pillar[5]arenes (P5As) formed by combining two distinct macrocycles with planar chiralities: paracyclophane units (<i>S</i><sub><i>p</i></sub> and <i>R</i><sub><i>p</i></sub>) and P5A macrocycles (<i>pS</i> and <i>pR</i>). These hexacyclic P5As were diastereoselectively synthesized using different paracyclophane units. The paracyclophane monomer bearing a ten-methylene (–CH<sub>2</sub>–)<sub>10</sub> alkyl loop shows dynamic planar chirality and presents as a racemate. This paracyclophane monomer undergoes diastereoselective cyclization to give two hexacyclic P5A diastereomers from 68 possible diastereomeric pairs of enantiomers. The paracyclophane monomer with a nine-methylene (–CH<sub>2</sub>–)<sub>9</sub> alkyl loop shows static planar chirality, and thus enantiopure <i>S</i><sub><i>p</i></sub> and <i>R</i><sub><i>p</i></sub> paracyclophane monomers can be separated by chiral column chromatography. The hexacyclic chiral P5As with all <i>S</i><sub><i>p</i></sub>-<i>pS</i> and <i>R</i><sub><i>p</i></sub>-<i>pR</i> cyclic units can be exclusively obtained from eight possible diastereomers when using the enantiopure <i>S</i><sub><i>p</i></sub> and <i>R</i><sub><i>p</i></sub> paracyclophane monomers, respectively. These hexacyclic chiral P5As exhibited stable chirality due to their self-locked structures arising from the communication of these chiral cyclic units and displayed unique chiroptical properties due to the communication between the unit and macrocyclic chirality.</p>

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Stereochemically self-locked hexacyclic chiral pillar[5]arenes: unit and macrocyclic planar chirality interplay for their diastereoselective synthesis and chiroptical properties

  • 期刊论文

  • 发表日期：

    2026年1月15日

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  • De-Hui Tuo,
  • Shigehisa Akine,
  • Kenichi Kato,
  • Shunsuke Ohtani,
  • Tomoki Ogoshi

摘要

The synthesis of specific multicyclic chiral macrocycles from other multiple possible isomers and constructing communication systems among their chiral cyclic units remain challenging. We herein report a series of hexacyclic chiral pillar[5]arenes (P5As) formed by combining two distinct macrocycles with planar chiralities: paracyclophane units (Sp and Rp) and P5A macrocycles (pS and pR). These hexacyclic P5As were diastereoselectively synthesized using different paracyclophane units. The paracyclophane monomer bearing a ten-methylene (–CH2–)10 alkyl loop shows dynamic planar chirality and presents as a racemate. This paracyclophane monomer undergoes diastereoselective cyclization to give two hexacyclic P5A diastereomers from 68 possible diastereomeric pairs of enantiomers. The paracyclophane monomer with a nine-methylene (–CH2–)9 alkyl loop shows static planar chirality, and thus enantiopure Sp and Rp paracyclophane monomers can be separated by chiral column chromatography. The hexacyclic chiral P5As with all Sp-pS and Rp-pR cyclic units can be exclusively obtained from eight possible diastereomers when using the enantiopure Sp and Rp paracyclophane monomers, respectively. These hexacyclic chiral P5As exhibited stable chirality due to their self-locked structures arising from the communication of these chiral cyclic units and displayed unique chiroptical properties due to the communication between the unit and macrocyclic chirality.