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Construction of visible-light-responsive coordination cages toward unprecedented photoreactions

Research Project

Project/Area Number 19K15581
Research Category

Grant-in-Aid for Early-Career Scientists

Allocation TypeMulti-year Fund
Review Section Basic Section 34010:Inorganic/coordination chemistry-related
Research InstitutionThe University of Tokyo

Principal Investigator

Takezawa Hiroki  東京大学, 大学院工学系研究科(工学部), 助教 (60813897)

Project Period (FY) 2019-04-01 – 2021-03-31
Project Status Completed (Fiscal Year 2020)
Budget Amount *help
¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000)
Fiscal Year 2020: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000)
Fiscal Year 2019: ¥2,210,000 (Direct Cost: ¥1,700,000、Indirect Cost: ¥510,000)
Keywords自己組織化 / 可視光反応 / ホスト-ゲスト / 錯体化学 / 配座固定 / 有機合成化学 / 分子認識 / ホスト-ゲスト
Outline of Research at the Start

反応基質の配座・立体環境を制御可能な中空錯体に対し可視光応答部位(光増感部位)を組み込んだ新奇可視光応答性中空錯体を合成する。この中空錯体を用い、通常の条件では合成困難な化合物を、前駆体の配座制御によって単工程で合成する手法を実現する。また、本研究で開発した反応系を高い歪みをもつ環状化合物や高度に修飾された基質の立体選択的合成へと展開する。

Outline of Final Research Achievements

In this work, visible-light responsive host complexes with molecular recognition ability have been synthesized. Simple mixing of a visible-light responsive Ru(II) or Ir(III) complex, a Pd(II) or Pt(II) complex, and a tripodal ligand in a 3:3:4 ratio gave self-assembled coordination cages with visible-light-induced catalytic activities. The cages efficiently catalyzed E-Z isomerizations and oxidative cleavages of olefins rather than common photoredox catalysts such as (bpy)3Ru.

Academic Significance and Societal Importance of the Research Achievements

可視光(蛍光灯や太陽光)を用いた有機反応は、物質合成に必要なエネルギーを抑えるのみならず、副生成物の少ないクリーンな反応としても意義深い。可視光応答性の触媒は一般に基質から離れて作用するため、反応の効率や選択性が低いことも多い。本研究では、高効率・高選択性の可視光反応を、標的基質の包接ができる中空錯体を用いて実現する新しい手法を開発した。可視光反応の応用範囲を広げる一歩となる。

Report

(3 results)
  • 2020 Annual Research Report   Final Research Report ( PDF )
  • 2019 Research-status Report
  • Research Products

    (27 results)

All 2021 2020 2019

All Journal Article (5 results) (of which Peer Reviewed: 5 results,  Open Access: 3 results) Presentation (21 results) (of which Int'l Joint Research: 2 results,  Invited: 1 results) Patent(Industrial Property Rights) (1 results)

  • [Journal Article] Confinement of Water-Soluble Cationic Substrates in a Cationic Molecular Cage by Capping the Portals with Tripodal Anions2020

    • Author(s)
      Takezawa Hiroki、Tabuchi Ryosuke、Sunohara Haruka、Fujita Makoto
    • Journal Title

      Journal of the American Chemical Society

      Volume: 142 Issue: 42 Pages: 17919-17922

    • DOI

      10.1021/jacs.0c08835

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Enhanced reactivity of twisted amides inside a molecular cage2020

    • Author(s)
      Takezawa Hiroki、Shitozawa Kosuke、Fujita Makoto
    • Journal Title

      Nature Chemistry

      Volume: 12 Issue: 6 Pages: 574-578

    • DOI

      10.1038/s41557-020-0455-y

    • Related Report
      2020 Annual Research Report 2019 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] A Robust Double-walled Knotted Cage Revealed Guest Binding through Adaptive Portal Expansion2020

    • Author(s)
      Tamura Yukari、Takezawa Hiroki、Fujita Makoto
    • Journal Title

      Chemistry Letters

      Volume: 49 Issue: 8 Pages: 912-914

    • DOI

      10.1246/cl.200282

    • NAID

      130007884737

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] A Double-Walled Knotted Cage for Guest-Adaptive Molecular Recognition2020

    • Author(s)
      Tamura Yukari、Takezawa Hiroki、Fujita Makoto
    • Journal Title

      Journal of the American Chemical Society

      Volume: 142 Issue: 12 Pages: 5504-5508

    • DOI

      10.1021/jacs.0c00459

    • Related Report
      2019 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Demethylenation of Cyclopropanes via Photoinduced Guest‐to‐Host Electron Transfer in an M 6 L 4 Cage2019

    • Author(s)
      Cullen William、Takezawa Hiroki、Fujita Makoto
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 58 Issue: 27 Pages: 9171-9173

    • DOI

      10.1002/anie.201904752

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Presentation] Controlled Cyclization of Arylalkynes through Folding inside a Molecular Cage2021

    • Author(s)
      Hiroki Takezawa, Harumi Hayakawa, Makoto Fujita
    • Organizer
      日本化学会第101春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] Dynamic behavior of double-walled cages in the self-assembly and the guest recognition2021

    • Author(s)
      Yukari Tamura, Hiroki Takezawa, Makoto Fujita
    • Organizer
      日本化学会第101春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] Diastereoselective pericyclic cascades of linear terpenoids through conformational control in a bowl-shaped host2021

    • Author(s)
      Tomoya Kanda, Hiroki Takezawa, Makoto Fujita
    • Organizer
      日本化学会第101春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] 可視光応答性 Ir/Pt 中空ホスト錯体の構築と効率的可視光反応2021

    • Author(s)
      春原 晴香、竹澤 浩気、藤田 誠
    • Organizer
      日本化学会第101春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] ルイス塩基部位を持つ蓋状アニオンのかご型錯体への付与とゲスト包接促進2021

    • Author(s)
      谷口 旺、春原 晴香、竹澤 浩気、藤田 誠
    • Organizer
      日本化学会第101春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] 三脚型蓋状アニオンによるカチオン性かご型錯体へのカチオン包接と構造制御2021

    • Author(s)
      田淵 凌輔、竹澤 浩気、藤田 誠
    • Organizer
      日本化学会第101春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] 光・酸化還元活性中空錯体の構築に向けた含カルバゾール配位子の合成2021

    • Author(s)
      川口 悠伍、田村 有佳梨、竹澤 浩気、藤田 誠
    • Organizer
      日本化学会第101春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] 中空錯体への包接による芳香族化合物とアルデヒドの縮合反応制御2021

    • Author(s)
      飯塚 健太、竹澤 浩気、藤田 誠
    • Organizer
      日本化学会第101春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] Stereoselective cascade cyclization of linear terpenoids using a bowl-shaped host2020

    • Author(s)
      Tomoya Kanda, Hiroki Takezawa, Makoto Fujita
    • Organizer
      錯体化学会 第70回討論会
    • Related Report
      2020 Annual Research Report
  • [Presentation] 中空錯体への閉じ込めによる分子操作と反応精密制御2020

    • Author(s)
      竹澤 浩気
    • Organizer
      錯体化学若手の会 第18回 Web勉強会
    • Related Report
      2020 Annual Research Report
    • Invited
  • [Presentation] 可視光応答性イリジウム多核ホスト錯体の自己集合構築と光反応への展開2020

    • Author(s)
      春原 晴香、小山田 健太、竹澤 浩気、藤田誠
    • Organizer
      日本化学会第100春季年会
    • Related Report
      2019 Research-status Report
  • [Presentation] かご型錯体空孔における共包接を利用したアミドのねじれ誘起加水分解2020

    • Author(s)
      志渡澤 幸佑、竹澤 浩気、藤田 誠
    • Organizer
      日本化学会第100春季年会
    • Related Report
      2019 Research-status Report
  • [Presentation] Guest-adaptive molecular recognition by a double-walled coordination cage2020

    • Author(s)
      田村 有佳梨、竹澤 浩気、藤田 誠
    • Organizer
      日本化学会第100春季年会
    • Related Report
      2019 Research-status Report
  • [Presentation] 蓋状アニオンによるかご型錯体の分子包接能拡張2020

    • Author(s)
      田淵 凌輔、春原 晴香、竹澤 浩気、藤田 誠
    • Organizer
      日本化学会第100春季年会
    • Related Report
      2019 Research-status Report
  • [Presentation] 空孔包接による直鎖状テルペノイドの配座制御と熱的環化反応2020

    • Author(s)
      神田 智哉、竹澤 浩気、藤田 誠
    • Organizer
      日本化学会第100春季年会
    • Related Report
      2019 Research-status Report
  • [Presentation] 中空錯体への包接を利用したポリインの配座固定と環化反応制御2020

    • Author(s)
      早川 遥海、神田 智哉、竹澤 浩気、藤田 誠
    • Organizer
      日本化学会第100春季年会
    • Related Report
      2019 Research-status Report
  • [Presentation] Amide Activation by Twistingin a Coordination Cage2019

    • Author(s)
      Hiroki Takezawa, Makoto Fujita
    • Organizer
      7th Asian Conference on Coordination Chemistry
    • Related Report
      2019 Research-status Report
    • Int'l Joint Research
  • [Presentation] Adaptive and Dynamic Guest Binding by a Double-Walled Knotted Cage2019

    • Author(s)
      Yukari Tamura, Hiroki Takezawa, Makoto Fujita
    • Organizer
      錯体化学会 第69回討論会
    • Related Report
      2019 Research-status Report
  • [Presentation] Heterometallic Coordination Cages with Visible Light Responsive Moieties at the Vertexes2019

    • Author(s)
      Haruka Sunohara, Hiroki Takezawa, Makoto Fujita
    • Organizer
      錯体化学会 第69回討論会
    • Related Report
      2019 Research-status Report
  • [Presentation] かご型錯体への包接によるアミドのねじれ誘起と活性化2019

    • Author(s)
      志渡澤 幸佑、竹澤 浩気、藤田 誠
    • Organizer
      錯体化学会 第69回討論会
    • Related Report
      2019 Research-status Report
  • [Presentation] Selective Electrophilic Reactions of Flexible Terpenoids through Conformational Fixing in a Confined Cavity2019

    • Author(s)
      Tomoya Kanda, Hiroki Takezawa, Makoto Fujita
    • Organizer
      7th Asian Conference on Coordination Chemistry
    • Related Report
      2019 Research-status Report
    • Int'l Joint Research
  • [Patent(Industrial Property Rights)] ホスト分子の包接能の変更方法、包接体の製造方法、包接体、単結晶、複合体、及び標的分子捕捉用キット2021

    • Inventor(s)
      藤田 誠、竹澤 浩気
    • Industrial Property Rights Holder
      藤田 誠、竹澤 浩気
    • Industrial Property Rights Type
      特許
    • Filing Date
      2021
    • Related Report
      2020 Annual Research Report

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Published: 2019-04-18   Modified: 2022-01-27  

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