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Development of highly active organic molecular catalysts for hydrogen extract-release from biologically produced organic materials

Research Project

Project/Area Number 20K05473
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Review Section Basic Section 33010:Structural organic chemistry and physical organic chemistry-related
Research InstitutionTokyo University of Agriculture and Technology

Principal Investigator

Okamoto Akiko  東京農工大学, 工学(系)研究科(研究院), 講師 (30512777)

Project Period (FY) 2020-04-01 – 2024-03-31
Project Status Completed (Fiscal Year 2023)
Budget Amount *help
¥4,420,000 (Direct Cost: ¥3,400,000、Indirect Cost: ¥1,020,000)
Fiscal Year 2022: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Fiscal Year 2021: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000)
Fiscal Year 2020: ¥1,040,000 (Direct Cost: ¥800,000、Indirect Cost: ¥240,000)
Keywords有機分子触媒 / 水素引き抜き-放出 / 酸化還元能 / 非共平面的芳香環集積分子 / peri-アロイルナフタレン / 高歪ピナコール / 分子立体構造解析 / ピナコール / 水素引き抜き-放出 / 非共平面性 / 高歪み / 空間構造解析 / 水素引き抜きー放出 / 糖
Outline of Research at the Start

本研究では多波長の光照射下で未利用の生物産出有機物質(糖類等)から水素を引き抜き放出する有機分子触媒を創出する。従来の酸化還元型有機分子触媒は酵素や色素の酸化還元部位を組み込んだものが多く,基質の適用範囲は限られていた。本研究では,酸化還元能を変化させるための新たなパラダイムとして,結合形成・解裂点周辺の芳香環の空間配置が「非共平面的で, 強固に固定されていない」有機分子の利用を追求する。具体的には非共平面的で可動なアロイル基を持つジケトンと高歪ジオールを対象に,反応挙動の解析と分子立体構造の整理を行い,「酸化還元能が調節可能な」全く新しい概念の有機分子触媒のカテゴリーの創造を目指す。

Outline of Final Research Achievements

In order to develop novel organic molecular catalyst that adjusts the redox ability by changing the molecular three-dimensional structure, understanding the spatial structure of naphthalene diketone compounds and diol compounds, and investigation of the reduction-oxidation reaction behavior of the diketone-diol pairs have carried out. First, various diketone compounds were synthesized, and the correlation between molecular modification and changes in the steric environment near the carbonyl groups was derived from the various conformations in the crystal. Furthermore, the diol compounds are stabilized in solution by adopting a conformation that accumulates intramolecular hydrogen bonds. Next, the reaction behavior analysis has revealed the correlation between spatial organization and reactivity, i.e. the closely flexible carbonyl configuration of the diketone compound is linked to the ease of reduction, and the increased strain of the diol is linked to the ease of oxidation.

Academic Significance and Societal Importance of the Research Achievements

遷移金属と異なり有機分子は酸化数を多様に変化させられない。その課題を解決すべく既存の酸化還元型有機分子触媒は酵素や色素の酸化還元部位を組み込んでいるが基質の適用範囲は限られる。本研究では酸化還元能を変化させるための新たなパラダイムとして,結合形成・解裂点周辺の芳香環の空間配置が「非共平面的で強固に固定されていない」有機分子の利用を追求した。非共平面的なジケトン化合物の空間構造の精密な把握と反応挙動の整理に基づき,分子立体構造の変化が還元-酸化の受け易さと密接にリンクしていることを明らかにした。本成果は「酸化還元能を調節可能」な全く新しい概念の有機分子触媒のカテゴリーの創造に寄与するものである。

Report

(5 results)
  • 2023 Annual Research Report   Final Research Report ( PDF )
  • 2022 Research-status Report
  • 2021 Research-status Report
  • 2020 Research-status Report
  • Research Products

    (16 results)

All 2023 2021 Other

All Journal Article (7 results) (of which Peer Reviewed: 7 results,  Open Access: 5 results) Presentation (3 results) Remarks (6 results)

  • [Journal Article] Weak Interaction Based Interpretation of Crystal Packing Characteristics of Aromatic Rings Accumulating Molecules: Hirshfeld Surface Analyses Reinforced X-ray Crystal Study on 1,8-Dibenzoyl-7-Ethoxynaphthalen-2-ol and Its 2-Ethoxylated Homologue2023

    • Author(s)
      Iida Kikuko、Doi Taiki、Isogai-Koda Atsumi、Noguchi Keiichi、Yonezawa Noriyuki、Okamoto Akiko
    • Journal Title

      Journal of Chemical Crystallography

      Volume: 53 Issue: 4 Pages: 483-499

    • DOI

      10.1007/s10870-023-00987-z

    • Related Report
      2023 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Packing structure and non-classical hydrogen bonding interactions of the toluene solvate crystal of 1,8-bis(4-methylbenzoyl)naphthalene-2,7- diyl dibenzoate: Role of toluene molecule in determination of the spatial arrangement of the major constituent molecules2023

    • Author(s)
      M. Kobayashi, R. Sakamoto, P. Zhang, Y. Zhao, K. Li, K. Noguchi, N. Yonezawa and A. Okamoto
    • Journal Title

      Molecular Crystals and Liquid Crystals

      Volume: 757 Issue: 1 Pages: 107-124

    • DOI

      10.1080/15421406.2022.2141059

    • Related Report
      2022 Research-status Report
    • Peer Reviewed
  • [Journal Article] The crystal structure of 1,8-bis(4-methoxybenzoyl)naphthalene-2,7-diyl dibenzoate, C40H28O82021

    • Author(s)
      Miyuki Kobayashi, Kikuko Iida, Hiroaki Iitsuka, Kun Li, Noriyuki Yonezawa, Akiko Okamoto
    • Journal Title

      Zeitschrift fur Kristallographie-New Crystal Structures

      Volume: 236 Issue: 5 Pages: 945-947

    • DOI

      10.1515/ncrs-2021-0160

    • Related Report
      2021 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Distinguishment of Weak Interactions of Hydrogen Atoms Bound to Carbon Atoms: X-Ray Crystal Structural and Hirshfeld Surface Analyses of 2-Hydroxy-7-methoxy-3-(2,4,6-trimethylbenzoyl)naphthalene with the 2-Methoxylated Homologue2021

    • Author(s)
      Kikuko Iida, Toyokazu Muto, Miyuki Kobayashi, Hiroaki Iitsuka, Kun Li, Noriyuki Yonezawa* and Akiko Okamoto
    • Journal Title

      Letters in Organic Chemistry

      Volume: - Issue: 9 Pages: 757-765

    • DOI

      10.2174/1570178619666211231105233

    • Related Report
      2021 Research-status Report
    • Peer Reviewed
  • [Journal Article] The crystal structure of (1R*,2S*)-1,2-bis (2-fluorophenyl)-3,8-dimethoxyacenaphthene- 1,2-diol, C26H20F2O42021

    • Author(s)
      Hiroaki Iitsuka, Kun Li, Miyuki Kobayashi, Kikuko Iida, Keiichi Noguchi, Noriyuki Yonezawa, Akiko Okamoto
    • Journal Title

      Zeitschrift fur Kristallographie-New Crystal Structures

      Volume: 236 Issue: 6 Pages: 1301-1304

    • DOI

      10.1515/ncrs-2021-0314

    • Related Report
      2021 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Crystal structure of 1,2-bis(4-fluorophenyl)-1-hydroxy-2,3,8-trimethoxyacenaphthene: formation of a five-membered intramolecular O-H...O hydrogen-bonded ring2021

    • Author(s)
      Hiroaki Iitsuka,Kun Li,Miyuki Kobayashi,Kikuko Iida,Noriyuki Yonezawa,Akiko Okamoto
    • Journal Title

      Acta Crystallographica Section E Crystallographic Communications

      Volume: 77 Issue: 2 Pages: 175-179

    • DOI

      10.1107/s2056989021000669

    • Related Report
      2020 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Crystal structure of bis(1,8-dibenzoyl-7-methoxynaphthalen-2-yl) terephthalate: Terephthalate phenylene moiety acts as bidentate hydrogen acceptor of bidirectional C-H...pi classical hydrogen bonds2021

    • Author(s)
      Kikuko Iida,Rei Sakamoto,Kun Li, Miyuki Kobayashi,Hiroaki Iitsuka,Noriyuki Yonezawa,Akiko Okamoto
    • Journal Title

      European Journal of Chemistry

      Volume: 12 Issue: 2 Pages: 147-153

    • DOI

      10.5155/eurjchem.12.2.147-153.2114

    • Related Report
      2020 Research-status Report
    • Peer Reviewed / Open Access
  • [Presentation] peri-アロイルナフタレン化合物の還元的カップリング反応挙動と空間構造の相関2023

    • Author(s)
      堀健太,李坤,岡本昭子
    • Organizer
      第85回有機合成化学協会関東シンポジウム-新潟シンポジウム-
    • Related Report
      2023 Annual Research Report
  • [Presentation] (1R*,2S*)-1,2-ジアリール-1,2-アセナフテンジオール 類縁化合物の結晶構造:古典的水素結合で結ばれた 独立分子の会合体とその集積構造2021

    • Author(s)
      ◯李坤・御堂天啓・飯塚宏明・趙 一鳴・野口 恵一・渡辺 敏行・米澤 宣行・岡本 昭子
    • Organizer
      第29回有機結晶シンポジウム (P-7: ポスター発表)
    • Related Report
      2021 Research-status Report
  • [Presentation] 分子内架橋したperi-アロイルナフタレン化合物の結晶構造:ケトンの酸素原子と水分子で構築された椅子型配座の環状水六量体2021

    • Author(s)
      ◯岡本昭子・尾形和樹・御堂天啓・李坤・趙一鳴・野口恵一・渡辺敏行・米澤宣行
    • Organizer
      第29回有機結晶シンポジウム (O-16:口頭発表)
    • Related Report
      2021 Research-status Report
  • [Remarks] Researchmap

    • URL

      https://researchmap.jp/Akiko_okamoto

    • Related Report
      2023 Annual Research Report 2022 Research-status Report
  • [Remarks] 東京農工大学大学院応用化学専攻 渡辺・岡本研究室ホームページ

    • URL

      http://web.tuat.ac.jp/~yonezawa/

    • Related Report
      2023 Annual Research Report
  • [Remarks] 東京農工大学大学院応用化学専攻有機材料化学専修 渡辺・岡本研究室ホームページ

    • URL

      http://web.tuat.ac.jp/~yonezawa/

    • Related Report
      2022 Research-status Report 2021 Research-status Report 2020 Research-status Report
  • [Remarks] 東京農工大学 工学研究院 応用化学部門 岡本 昭子

    • URL

      https://kenkyu-web.tuat.ac.jp/Profiles/29/0002821/profile.html

    • Related Report
      2021 Research-status Report
  • [Remarks] researchmap 岡本 昭子

    • URL

      https://researchmap.jp/Akiko_okamoto

    • Related Report
      2021 Research-status Report
  • [Remarks] 東京農工大学 工学研究院 応用化学部門 岡本 昭子

    • URL

      https://kenkyu-web.tuat.ac.jp/Profiles/29/0002821/profile.html

    • Related Report
      2020 Research-status Report

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Published: 2020-04-28   Modified: 2025-01-30  

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