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Development of novel carbon source recycle reaction driven by visible light with water as electron source

Research Project

Project/Area Number 19H02735
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Review Section Basic Section 34010:Inorganic/coordination chemistry-related
Research InstitutionKyushu University

Principal Investigator

Shimakoshi Hisashi  九州大学, 工学研究院, 教授 (00284539)

Project Period (FY) 2019-04-01 – 2022-03-31
Project Status Completed (Fiscal Year 2021)
Budget Amount *help
¥17,420,000 (Direct Cost: ¥13,400,000、Indirect Cost: ¥4,020,000)
Fiscal Year 2021: ¥4,550,000 (Direct Cost: ¥3,500,000、Indirect Cost: ¥1,050,000)
Fiscal Year 2020: ¥6,370,000 (Direct Cost: ¥4,900,000、Indirect Cost: ¥1,470,000)
Fiscal Year 2019: ¥6,500,000 (Direct Cost: ¥5,000,000、Indirect Cost: ¥1,500,000)
Keywords酸化チタン / 光触媒 / ビタミンB12 / 有機塩素化合物 / 炭素資源リサイクル / 可視光応答型触媒 / カーボンリサイクル反応 / アミド化反応 / 可視光 / 脱ハロゲン化反応 / 炭素資源循環 / 有機ハロゲン化合物 / リサイクル反応 / ベースメタル / 脱塩素化反応 / 光増感剤
Outline of Research at the Start

本研究では、従来環境汚染物質として扱われてきた有機ハロゲン化合物を炭素資源と見なし、これを原料としてエステルやアミド化合物等の有用化成品合成を行い、負の遺産を有用なファインケミカルに変換するという、従来法とは異なる視点に立った新しい炭素資源リサイクル型反応の開発を行うことを目的とする。触媒としては、金属酵素の活性中心を模倣した金属錯体に光応答性ナノ粒子を複合化したハイブリッド型光触媒を作製し、光エネルギーを駆動力とする反応系を構築する。さらに光合成における二段階光励起Zスキーム機構を導入した新規な触媒システムを構築し、水を電子源とする可視光応答型の物質変換システムの確立までを目指す。

Outline of Final Research Achievements

In this study, as a method of recycling carbon resources, we developed a carbon resource recycling reaction in which organic halogen compounds, which are environmental pollutants, are dehalogenated and the remaining carbon part is used as a carbon source for useful compounds. As a method for this, we focused on the excellent properties of natural metal enzymes, synthesized a model complex that reproduces its function, and combined it with a photocatalyst to synthesize an environment-friendly catalyst that uses light energy as a driving force. We also succeeded in developing a hybrid catalyst that combines two types of photosensitizers and a vitamin B12 complex that serves as a catalyst site as a catalyst system that introduces a two-step photoexcitation Z scheme mechanism.

Academic Significance and Societal Importance of the Research Achievements

近年、天然酵素に光応答性、耐久性、外部刺激応答性などの新たな機能を付加したバイオインスパイード型人工酵素の研究が活発に行われている。金属酵素を例にすると、活性中心のモデルとなる金属錯体を電極、酸化物半導体および光増感剤などと複合化することで、電気化学的または光化学的に駆動する人工金属酵素の研究が目覚ましく発展している。一方で、これらの研究から、実用化に直結する汎用性の高い反応開発に至った例が未だ少ないのも現状である。本研究は、このような現状を打破すべく、バイオインスパイード型の触媒研究を一歩前に進め、社会実装に向けた新規で有用な炭素資源リサイクル型の物質変換システムの開発を行った。

Report

(4 results)
  • 2021 Annual Research Report   Final Research Report ( PDF )
  • 2020 Annual Research Report
  • 2019 Annual Research Report
  • Research Products

    (21 results)

All 2022 2021 2020 2019

All Journal Article (8 results) (of which Peer Reviewed: 8 results) Presentation (9 results) (of which Int'l Joint Research: 4 results,  Invited: 7 results) Book (4 results)

  • [Journal Article] Bioinspired Electrolysis for Green Molecular Transformations of Organic Halides Catalyzed by B12 Complex2021

    • Author(s)
      Hisashi Shimakoshi, Yoshio Hisaeda
    • Journal Title

      THE CHEMICAL RECORD

      Volume: 21 Issue: 9 Pages: 2080-2094

    • DOI

      10.1002/tcr.202100077

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Electrochemical Synthesis of Cyanoformamides from Trichloroacetonitrile and Secondary Amines Mediated by the B12 Derivative2021

    • Author(s)
      Mohammad Moniruzzaman, Yoshio Yano, Toshikazu Ono, Kenji Imamura, Yoshihito Shiota, Kazunari Yoshizawa, Yoshio Hisaeda, Hisashi Shimakoshi
    • Journal Title

      J. Org. Chem.

      Volume: 86 Issue: 22 Pages: 16134-16143

    • DOI

      10.1021/acs.joc.1c00837

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] One-Pot Synthesis of Tertiary Amides from Organic Trichlorides through Oxygen Atom Incorporation from Air by Convergent Paired Electrolysis2021

    • Author(s)
      Zhongli Luo, Kenji Imamura, Yoshihito Shiota, Kazunari Yoshizawa, Yoshio Hisaeda, Hisashi Shimakoshi
    • Journal Title

      J. Org. Chem.

      Volume: 86 Issue: 8 Pages: 5983-5990

    • DOI

      10.1021/acs.joc.1c00161

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Aerobic Electrochemical Transformations of DDT to Oxygen-Incorporated Products Catalyzed by a B12 Derivative2021

    • Author(s)
      Mohammad Moniruzzaman, Yoshio Yano, Toshikazu Ono, Yoshio Hisaeda, Hisashi Shimakoshi
    • Journal Title

      Bull. Chem. Soc. Jpn.

      Volume: 94 Issue: 11 Pages: 2784-2791

    • DOI

      10.1246/bcsj.20210316

    • NAID

      130008137575

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Catalytic Dehalogenation of Aryl Halides via Excited State Electron Transfer from the Co(I) State of B12 Complex2020

    • Author(s)
      Hisashi Shimakoshi, Keita Shichijo, Shiori Tominaga, Yoshio Hisaeda, Mamoru Fujitsuka, Tetsuro Majima
    • Journal Title

      Chemistry Letters

      Volume: 49 Issue: 7 Pages: 820-822

    • DOI

      10.1246/cl.200241

    • NAID

      130007872572

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis of a B12-BODIPY Dyad for B12-Inspired Photochemical Transformations of a Trichloromethylated Organic Compound2020

    • Author(s)
      Yuki Anai, Keita Chichijo, Mamoru Fujitsuka, Yoshio Hisaeda, Hisashi Shimakoshi
    • Journal Title

      Chemical Communications

      Volume: 56 Issue: 80 Pages: 11945-11948

    • DOI

      10.1039/d0cc04274a

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Visible light-driven photocatalytic duet reaction catalyzed by the B12-rhodium-titanium oxide hybrid catalyst2020

    • Author(s)
      Shichijo Keita、Fujitsuka Mamoru、Hisaeda Yoshio、Shimakoshi Hisashi
    • Journal Title

      Journal of Organometallic Chemistry

      Volume: 907 Pages: 121058-121058

    • DOI

      10.1016/j.jorganchem.2019.121058

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Visible light-driven cross-coupling reactions of alkyl halides with phenylacetylene derivatives for C(sp3)?C(sp) bond formation catalyzed by a B12 complex2019

    • Author(s)
      Chen Li、Kametani Yohei、Imamura Kenji、Abe Tsukasa、Shiota Yoshihito、Yoshizawa Kazunari、Hisaeda Yoshio、Shimakoshi Hisashi
    • Journal Title

      Chemical Communications

      Volume: 55 Issue: 87 Pages: 13070-13073

    • DOI

      10.1039/c9cc06185a

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Presentation] Bioinspired Catalytic Reactions With and Beyond the Vitamin B12 Function2021

    • Author(s)
      Hisashi Shimakoshi
    • Organizer
      JBNU International On-Line Symposium
    • Related Report
      2021 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] 光や電気エネルギーで駆動するビタミンB12誘導体による人工触媒システムの開発2021

    • Author(s)
      嶌越 恒
    • Organizer
      日本ビタミン学会第73回大会
    • Related Report
      2021 Annual Research Report
    • Invited
  • [Presentation] B12-BODIPY as visible light driven bioorganometallic catalyst2021

    • Author(s)
      Hisashi Shimakoshi
    • Organizer
      Pacifichem2020
    • Related Report
      2021 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] スチレン誘導体、ハロアセトニトリル、酸素の三元反応によるガンマ-ケトニトリルの可視光駆動型合成2021

    • Author(s)
      勝山陽菜、七條慶太、久枝良雄、嶌越 恒
    • Organizer
      第54回酸化反応討論会
    • Related Report
      2021 Annual Research Report
  • [Presentation] Fine Chemical Synthesis via Quinone Intermediate Using Catecholase Activity of Cu Complex2020

    • Author(s)
      Hisashi Shimakoshi
    • Organizer
      The 14th International Symposium on Organic Reactions
    • Related Report
      2020 Annual Research Report
    • Invited
  • [Presentation] トリクロロアセトニトリルからシアノ置換各種アミド化合物へのワンポット電解合成反応の開発2020

    • Author(s)
      嶌越恒、モハメッドモニルザマン、久枝良雄
    • Organizer
      第53回酸化反応討論会
    • Related Report
      2020 Annual Research Report
  • [Presentation] Bioinspired Organic Reactions Learned from Vitamin B12 Dependent Enzymes2020

    • Author(s)
      Hisashi Shimakoshi
    • Organizer
      UC Santa Barbara, Chemistry and Biochemistry, Fall 2020 Seminar
    • Related Report
      2020 Annual Research Report
    • Invited
  • [Presentation] Bioorganometallic B12 as Versatile Catalyst for Green Organic Synthesis2019

    • Author(s)
      Hisashi Shimakoshi
    • Organizer
      9th International Symposium on Bioorganometallic Chemistry
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Photo-driven B12 Inspired Reaction for Green Organic Synthesis2019

    • Author(s)
      Hisashi Shimakoshi
    • Organizer
      International Conference on Photocatalysis and Photoenergy 2019
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research / Invited
  • [Book] Vitamis and Hormones2022

    • Author(s)
      Hisashi Shimakoshi
    • Total Pages
      504
    • Publisher
      Elsevier
    • ISBN
      9780323992237
    • Related Report
      2021 Annual Research Report
  • [Book] Sustainable and Functional Redox Chemistry2022

    • Author(s)
      Hisashi Shimakoshi
    • Total Pages
      500
    • Publisher
      RSC books
    • ISBN
      9781839162466
    • Related Report
      2021 Annual Research Report
  • [Book] 有機電解合成の新潮流2021

    • Author(s)
      嶌越恒、久枝良雄
    • Total Pages
      340
    • Publisher
      シーエムシー出版
    • ISBN
      9784781316260
    • Related Report
      2021 Annual Research Report
  • [Book] CSJ Current Review 38 光エネルギー変換における分子触媒の新展開2020

    • Author(s)
      嶌越恒
    • Total Pages
      176
    • Publisher
      化学同人
    • ISBN
      9784759813982
    • Related Report
      2020 Annual Research Report

URL: 

Published: 2019-04-18   Modified: 2023-01-30  

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