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Precise Design and Functionalization of Asymmetric Supramolecular Spaces: Predictable Asymmetric Reactions based on Molecular Adsorption

Research Project

Project/Area Number 16K13959
Research Category

Grant-in-Aid for Challenging Exploratory Research

Allocation TypeMulti-year Fund
Research Field Inorganic chemistry
Research InstitutionThe University of Tokyo

Principal Investigator

Shionoya Mitsuhiko  東京大学, 大学院理学系研究科(理学部), 教授 (60187333)

Project Period (FY) 2016-04-01 – 2019-03-31
Project Status Completed (Fiscal Year 2018)
Budget Amount *help
¥3,770,000 (Direct Cost: ¥2,900,000、Indirect Cost: ¥870,000)
Fiscal Year 2017: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000)
Fiscal Year 2016: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
Keywords不斉超空間 / エナンチオ選択的反応 / 多孔性超分子結晶 / 不斉分子認識 / 超分子金属錯体 / 触媒反応 / 超分子錯体 / 多孔性金属錯体 / 不斉吸着・認識・反応 / 多孔性結晶 / 超分子 / 不斉反応 / 金属錯体 / 分子認識
Outline of Final Research Achievements

This study aimed to establish synthetic methods of porous chiral crystals by utilizing self-assembly of helical macrocyclic trinuclear Pd(II) complexes, and to develop reaction spaces for asymmetric reactions which possibly allow highly specific adsorption of substrates and site- and face-selective molecular adsorption. Firstly, we have succeeded in face-selective adsorption of prochiral molecules by utilizing the ability of asymmetric reagents to bind selectively to only one site of enantiomerically-paired binding pockets. In this connection, it was also found that photo-induced olefin migration reactions take place in this nano-channel. Moreover, self-assembly of the same Pd(II) complexes was found to produce homochiral porous crystals in the presence of sugar derivatives. Asymmetric Diels Alder reactions took place, though the enantiomeric excess was rather low, in the nano-pocket space in this crystal.

Academic Significance and Societal Importance of the Research Achievements

中空構造を持つ多孔性配位高分子、ゼオライト、分子カプセル、ミセル・ベシクル等は、分子の吸着、変換、輸送の場を提供する優れた物質群である。本研究で開拓された多孔性結晶は、分子認識能を有する大環状金属錯体の自己集積化を利用して簡便に合成が可能であり、分子認識・捕捉能と触媒機能を兼ね備えた不斉反応場の開発に新しい学術的意義を与えるものである。本研究成果は、近接効果と配向効果に基づくエネルギー低減型の高選択的不斉反応につながるものであり、社会的意義も高い。

Report

(4 results)
  • 2018 Annual Research Report   Final Research Report ( PDF )
  • 2017 Research-status Report
  • 2016 Research-status Report
  • Research Products

    (14 results)

All 2018 2017 2016 Other

All Int'l Joint Research (2 results) Journal Article (2 results) (of which Peer Reviewed: 2 results,  Acknowledgement Compliant: 1 results) Presentation (8 results) (of which Int'l Joint Research: 5 results,  Invited: 5 results) Remarks (2 results)

  • [Int'l Joint Research] Indiana University(米国)

    • Related Report
      2017 Research-status Report
  • [Int'l Joint Research] University of Amsterdam(オランダ)

    • Related Report
      2016 Research-status Report
  • [Journal Article] Chiral metal-macrocycle frameworks: supramolecular chirality induction and helicity inversion of the helical macrocyclic structures2016

    • Author(s)
      Ryou Kubota, Shohei Tashiro and Mitsuhiko Shionoya
    • Journal Title

      Chemical Science

      Volume: 7 Issue: 3 Pages: 2217-2221

    • DOI

      10.1039/c5sc04570c

    • Related Report
      2016 Research-status Report
    • Peer Reviewed
  • [Journal Article] Non-Covalent Immobilisation of p-Toluenesulfonic Acid in a Porous Molecular Crystal for Size-Specific Acid-Catalysed Reactions2016

    • Author(s)
      S. Tashiro, H. Yonezawa, R. Kubota, T. Umeki, M. Shionya
    • Journal Title

      Chem. Commun.

      Volume: 52 Issue: 49 Pages: 7657-7660

    • DOI

      10.1039/c6cc02621d

    • Related Report
      2016 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Presentation] Metal-based Supramolecular Array, Space and Motion2018

    • Author(s)
      Mitsuhiko Shionoya
    • Organizer
      MANA International Symposium 2018 Towards Perceptive Nanomaterials, Devices and Systems
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Coordination Asymmetry based on Supramolecular Porous Crystals2018

    • Author(s)
      Mitsuhiko Shionoya
    • Organizer
      International Symposium on Macrocyclic and Supramolecular Chemistry
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Functionalization of Pd(II)-macrocycle-assembled core-shell porous crystals2018

    • Author(s)
      Shinya Mitsui, David Burke, Shohei Tashiro, Nobuyuki Matsushita, Mitsuhiko Shionoya
    • Organizer
      日本化学会第98春季年会
    • Related Report
      2017 Research-status Report
  • [Presentation] ハロゲン配位子が異なる同形の環状三核Pd(II)錯体集積型多孔性結晶を用いたコア/シェル型複合結晶の合成と細孔ハイブリッド化2017

    • Author(s)
      三井伸也、Burke David、田代省平、松下信之、塩谷光彦
    • Organizer
      第7回CSJ化学フェスタ2017
    • Related Report
      2017 Research-status Report
  • [Presentation] PdII マクロサイクル集積型コアーシェル結晶細孔内への色素分子の取り込みとその挙動2017

    • Author(s)
      三井伸也、田代省平、David Burke、松下信之、塩谷光彦
    • Organizer
      第67回錯体化学討論会
    • Related Report
      2017 Research-status Report
  • [Presentation] Dynamic Molecular Behaviors in Confined Supramolecular Spaces2017

    • Author(s)
      Mitsuhiko Shionoya
    • Organizer
      JPN-US bilateral meeting
    • Related Report
      2017 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] Metal-based Supramolecular Array, Space and Motion2016

    • Author(s)
      Mitsuhiko Shionoya
    • Organizer
      RSC Macrocyclic and Supramolecular Meeting (MASC-2016)
    • Place of Presentation
      Edinburgh (UK)
    • Year and Date
      2016-12-15
    • Related Report
      2016 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] Supramolecular Design for Metal Array, Space, and Motion2016

    • Author(s)
      Mitsuhiko Shionoya
    • Organizer
      Chile-Japan Academic Forum 2016
    • Place of Presentation
      Santiago (Chile)
    • Related Report
      2016 Research-status Report
    • Int'l Joint Research / Invited
  • [Remarks] 塩谷研究室:論文

    • URL

      http://www.chem.s.u-tokyo.ac.jp/users/bioinorg/index.html

    • Related Report
      2018 Annual Research Report
  • [Remarks] 塩谷研究室 Bioinorganic Chemistry Laboratory

    • URL

      http://www.chem.s.u-tokyo.ac.jp/users/bioinorg/index.html

    • Related Report
      2016 Research-status Report

URL: 

Published: 2016-04-21   Modified: 2022-02-22  

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