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Photoredox-catalyzed generation of reactive fluorinated species and their applications

Research Project

Project/Area Number 16H06038
Research Category

Grant-in-Aid for Young Scientists (A)

Allocation TypeSingle-year Grants
Research Field Synthetic chemistry
Research InstitutionTokyo Institute of Technology

Principal Investigator

Koike Takashi  東京工業大学, 科学技術創成研究院, 助教 (30451991)

Project Period (FY) 2016-04-01 – 2020-03-31
Project Status Completed (Fiscal Year 2019)
Budget Amount *help
¥25,480,000 (Direct Cost: ¥19,600,000、Indirect Cost: ¥5,880,000)
Fiscal Year 2019: ¥3,120,000 (Direct Cost: ¥2,400,000、Indirect Cost: ¥720,000)
Fiscal Year 2018: ¥3,120,000 (Direct Cost: ¥2,400,000、Indirect Cost: ¥720,000)
Fiscal Year 2017: ¥11,180,000 (Direct Cost: ¥8,600,000、Indirect Cost: ¥2,580,000)
Fiscal Year 2016: ¥8,060,000 (Direct Cost: ¥6,200,000、Indirect Cost: ¥1,860,000)
Keywords有機フッ素化合物 / 分子光触媒 / ラジカル反応 / 有機触媒 / 遷移金属触媒 / 光レドックス触媒作用 / 有機フッ素化学 / 可視光反応 / 酸化還元反応 / 有機化学 / 光触媒
Outline of Final Research Achievements

Trifluoromethyl (CF3), difluoromethyl (CF2H), and monofluoromethyl (CH2F) groups are versatile structural motifs, especially in the fields of pharmaceuticals, agrochemicals, and organic functional materials. Thus, development of new protocols for fluoromethylation of various skeletons has become a vital subject to be studied in the field of organic synthetic chemistry. For the past several years, photoredox catalysis has emerged as a useful tool for radical reactions through visible-light-induced single-electron-transfer (SET) processes. Here we have developed photocatalytic radical fluoromethylation for simple synthesis of valuable organofluorine compounds.

Academic Significance and Societal Importance of the Research Achievements

フッ素原子は、全元素中最大の電気陰性度を有し、その特異な性質から有機フッ素化合物の合成には、通常の合成戦略が通じないことが多く、簡便な新しい合成方法の開発がのぞまれている。本研究で開発した方法は、可視光、室温、汎用な実験器具で実施可能であるだけでなく、前例のない新規な有機フッ素化合物も短工程で合成できる。すなわち有機フッ素化合物合成に革新をもたらす成果が得られたと考える。また、これまで貴金属錯体光触媒が本研究分野では一般的に使用されてきたが、本研究では従来の触媒性能を超える有機分子光触媒の開発に成功した。本系の実用性を高め、グリーンケミストリーの観点からも大きなインパクトを与える成果である。

Report

(5 results)
  • 2019 Annual Research Report   Final Research Report ( PDF )
  • 2018 Annual Research Report
  • 2017 Annual Research Report
  • 2016 Annual Research Report
  • Research Products

    (56 results)

All 2020 2019 2018 2017 2016 Other

All Journal Article (16 results) (of which Peer Reviewed: 16 results,  Open Access: 4 results,  Acknowledgement Compliant: 3 results) Presentation (34 results) (of which Int'l Joint Research: 13 results,  Invited: 9 results) Remarks (4 results) Patent(Industrial Property Rights) (2 results)

  • [Journal Article] Fluoroalkanesulfinate Salts as Dual Fluoroalkyl and SO2 Sources: Atom-Economical Fluoroalkyl-Sulfonylation of Alkenes and Alkynes by Photoredox Catalysis2020

    • Author(s)
      Tanaka Seiya、Nakayama Yoshiki、Konishi Yusuke、Koike Takashi、Akita Munetaka
    • Journal Title

      Organic Letters

      Volume: 22 Issue: 7 Pages: 2801-2805

    • DOI

      10.1021/acs.orglett.0c00789

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Frontiers in Radical Fluoromethylation by Visible‐Light Organic Photocatalysis2020

    • Author(s)
      Koike Takashi
    • Journal Title

      Asian Journal of Organic Chemistry

      Volume: 9 Issue: 4 Pages: 529-537

    • DOI

      10.1002/ajoc.202000058

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Visible-Light Photoredox Catalysis: New Strategies for Radical Reactions2019

    • Author(s)
      Koike Takashi
    • Journal Title

      Journal of Synthetic Organic Chemistry, Japan

      Volume: 77 Issue: 5 Pages: 414-423

    • DOI

      10.5059/yukigoseikyokaishi.77.414

    • NAID

      130007645014

    • ISSN
      0037-9980, 1883-6526
    • Year and Date
      2019-05-01
    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Keto-Difluoromethylation of Aromatic Alkenes by Photoredox Catalysis: Step-Economical Synthesis of α-CF2H-Substituted Ketones in Flow2019

    • Author(s)
      Nakayama Yoshiki、Ando Gaku、Abe Manabu、Koike Takashi、Akita Munetaka
    • Journal Title

      ACS Catalysis

      Volume: 9 Issue: 7 Pages: 6555-6563

    • DOI

      10.1021/acscatal.9b01312

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Recent progress in photochemical radical di- and mono-fluoromethylation2019

    • Author(s)
      Koike Takashi、Akita Munetaka
    • Journal Title

      Organic & Biomolecular Chemistry

      Volume: 17 Issue: 22 Pages: 5413-5419

    • DOI

      10.1039/c9ob00734b

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Visible-Light-Triggered Monofluoromethylation of Alkenes by Strongly Reducing 1,4-Bis(diphenylamino)naphthalene Photoredox Catalysis2019

    • Author(s)
      Noto Naoki、Koike Takashi、Akita Munetaka
    • Journal Title

      ACS Catalysis

      Volume: 9 Issue: 5 Pages: 4382-4387

    • DOI

      10.1021/acscatal.9b00473

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] 18 Photocatalytic Introduction of Fluorinated Groups2019

    • Author(s)
      T. Koike, M. Akita
    • Journal Title

      Science of Synthesis: Photocatalysis in Organic Synthesis

      Volume: - Pages: 559-574

    • DOI

      10.1055/sos-sd-229-00316

    • ISBN
      9783132417021, 9783132417069
    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Strongly Reducing (Diarylamino)anthracene Catalyst for Metal-Free Visible-Light Photocatalytic Fluoroalkylation2018

    • Author(s)
      Noto Naoki、Tanaka Yuya、Koike Takashi、Akita Munetaka
    • Journal Title

      ACS Catalysis

      Volume: 8 Issue: 10 Pages: 9408-9419

    • DOI

      10.1021/acscatal.8b02885

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Photoredox radical C?H oxygenation of aromatics with aroyloxylutidinium salts2018

    • Author(s)
      Miyazawa Kazuki、Ochi Rika、Koike Takashi、Akita Munetaka
    • Journal Title

      Organic Chemistry Frontiers

      Volume: 5 Issue: 9 Pages: 1406-1410

    • DOI

      10.1039/c8qo00089a

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] New Horizons of Photocatalytic Fluoromethylative Difunctionalization of Alkenes2018

    • Author(s)
      Koike Takashi、Akita Munetaka
    • Journal Title

      Chem

      Volume: 4 Issue: 3 Pages: 409-437

    • DOI

      10.1016/j.chempr.2017.11.004

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Metal-free di- and tri-fluoromethylation of alkenes realized by visible-light-induced perylene photoredox catalysis2017

    • Author(s)
      Noto Naoki、Koike Takashi、Akita Munetaka
    • Journal Title

      Chemical Science

      Volume: 8 Issue: 9 Pages: 6375-6379

    • DOI

      10.1039/c7sc01703k

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Photoredox-catalyzed oxytrifluoromethylation of allenes: stereoselective synthesis of 2-trifluoromethylated allyl acetates2017

    • Author(s)
      Ren Tomita, Takashi Koike, Munetaka Akita
    • Journal Title

      Chemical Communications

      Volume: 53 Issue: 34 Pages: 4681-4684

    • DOI

      10.1039/c7cc01759f

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Combination of Organotrifluoroborates with Photoredox Catalysis Marking a New Phase in Organic Radical Chemistry2016

    • Author(s)
      Takashi Koike, Munetaka Akita
    • Journal Title

      Organic & Biomolecular Chemistry

      Volume: 14 Pages: 6886-6890

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Diastereoselective Synthesis of CF3- and CF2H‐Substituted Spiroethers from Aryl-Fused Cycloalkenylalkanols by Photoredox Catalysis2016

    • Author(s)
      Naoki Noto, Takashi Koike, Munetaka Akita
    • Journal Title

      The Journal of Organic Chemistry

      Volume: 81 Issue: 16 Pages: 7064-7071

    • DOI

      10.1021/acs.joc.6b00953

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] A Versatile Strategy for Difunctionalization of Carbon-Carbon Multiple Bonds by Photoredox Catalysis2016

    • Author(s)
      Takashi Koike, Munetaka Akita
    • Journal Title

      Organic Chemistry Frontiers

      Volume: 3 Issue: 10 Pages: 1345-1349

    • DOI

      10.1039/c6qo00139d

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Fine Design of Photoredox Systems for Catalytic Fluoromethylation of Carbon-Carbon Multiple Bonds2016

    • Author(s)
      Takashi Koike, Munetaka Akita
    • Journal Title

      Accounts of Chemical Research

      Volume: 49 Issue: 9 Pages: 1937-1945

    • DOI

      10.1021/acs.accounts.6b00268

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Open Access / Acknowledgement Compliant
  • [Presentation] Atom-Economical Sulfonyl-Fluoroalkylation of C-C Unsaturated Bonds by Ir Photoredox Catalysis2019

    • Author(s)
      Tanaka Seiya、Nakayama Yoshiki、Konishi Yusuke、Koike Takashi、Akita Munetaka
    • Organizer
      The 18th Asian Chemical Congress (ACC) and The 20th General Assembly of the Federation of Asian Chemical Societies (FACS)
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research
  • [Presentation] 高還元力を有する有機可視光レドックス触媒を用いたモノフルオロアルキルラジカル種の発生:β-フルオロケトン類の新合成法2019

    • Author(s)
      谷口 諒・納戸直木・小池隆司・穐田宗隆
    • Organizer
      第42回 フッ素化学討論会
    • Related Report
      2019 Annual Research Report
  • [Presentation] Visible-Light Photoredox Catalysis: New Strategies for Radical Reactions2019

    • Author(s)
      Koike Takashi
    • Organizer
      第69回 錯体化学討論会
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Design of Visible-Light Photoredox Systems for Metal-free Radical Fluoroalkylation2019

    • Author(s)
      Koike Takashi
    • Organizer
      2019年 光化学討論会
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Design of Photoredox Systems for Metal-Free Radical Fluoroalkylation2019

    • Author(s)
      Koike Takashi
    • Organizer
      2019 Gordon Research Conference: Light-Driven Reactions, Materials and Devices
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] フォトレドックス触媒を用いた炭素-炭素不飽和結合へのスルホニルトリフルオロメチル化反応の開発2019

    • Author(s)
      田中聖也・中山栄希・小西勇介・小池隆司・穐田宗隆
    • Organizer
      第43回 有機電子移動化学討論会
    • Related Report
      2019 Annual Research Report
  • [Presentation] フォトレドックス触媒を用いたアルケン類からのα-ジフルオロメチルケトンのフロー合成と官能基変換2018

    • Author(s)
      中山栄希・小池隆司・穐田宗隆
    • Organizer
      日本化学会 第99春季年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] 高還元力を有する有機フォトレドックス触媒によるモノフルオロアルキルラジカル種の発生を経たβ-フルオロケトン類の合成2018

    • Author(s)
      谷口諒・納戸直木・小池隆司・穐田宗隆
    • Organizer
      日本化学会 第99春季年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] フォトレドックス触媒を用いたアルケン類のスルホニルトリフルオロメチル化反応2018

    • Author(s)
      田中聖也・中山栄希・小西勇介・小池隆司・穐田宗隆
    • Organizer
      日本化学会 第99春季年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] Visible light-triggered monofluoromethylation of alkenes by strongly reducing organic photoredox catalysis2018

    • Author(s)
      N. Noto, T. Koike, M. Akita
    • Organizer
      日本化学会 第99春季年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] 有機光触媒を用いたアルケンのフルオロアルキル二官能基化反応2018

    • Author(s)
      納戸直木・小池隆司・穐田宗隆
    • Organizer
      第41回 フッ素化学討論会
    • Related Report
      2018 Annual Research Report
  • [Presentation] フローシステムを活用したオレフィン類の光触媒的ケト-ジフルオロメチル化反応2018

    • Author(s)
      中山栄希・安藤岳・小池隆司・穐田宗隆
    • Organizer
      第41回 フッ素化学討論会
    • Related Report
      2018 Annual Research Report
  • [Presentation] 多環芳香環を基盤とする有機光触媒によるフルオロアルキル化反応2018

    • Author(s)
      納戸直木・小池隆司・穐田宗隆
    • Organizer
      第122回 触媒討論会
    • Related Report
      2018 Annual Research Report
  • [Presentation] Design of Photoredox Systems for Catalytic Fluoromethylation of Alkenes2018

    • Author(s)
      T. Koike
    • Organizer
      The 1st Sino-Japanese Symposium on Catalysis for Precision Synthesis
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Design of Photoredox Systems for Catalytic Fluoroalkylation of Alkenes2018

    • Author(s)
      T. Koike
    • Organizer
      The 233rd ECS Meeting
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Study on Design and Mechanism of Metal-free Photocatalytic Fluoroalkylation of Olefins2018

    • Author(s)
      N. Noto・T. Koike・M. Akita
    • Organizer
      Beilstein Organic Chemistry Symposium 2018: Photoredox Catalysis for Novel Organic ReactionsBeilstein Organic Chemistry Symposium 2018: Photoredox Catalysis for Novel Organic Reactions
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research
  • [Presentation] フォトレドックス触媒によるアミジルラジカル種の発生を鍵とした芳香族直接アミド化反応2018

    • Author(s)
      大地里佳・宮澤和己・小池隆司・穐田宗隆
    • Organizer
      日本化学会 第98春季年会
    • Related Report
      2017 Annual Research Report
  • [Presentation] オレフィン類に対する光触媒的ケト-ジフルオロメチル化反応2018

    • Author(s)
      中山栄希・安藤岳・小池隆司・穐田宗隆
    • Organizer
      日本化学会 第98春季年会
    • Related Report
      2017 Annual Research Report
  • [Presentation] Metal-free Photocatalytic Fluoroalkylation of Olefins with Diarylaminoanthracene Catalysts2018

    • Author(s)
      Naoki Noto・Takashi Koike・Munetaka Akita
    • Organizer
      日本化学会 第98春季年会
    • Related Report
      2017 Annual Research Report
  • [Presentation] フォトレドックス触媒が拓く可視光駆動ラジカル官能基化2018

    • Author(s)
      小池隆司
    • Organizer
      日本化学会 第98春季年会
    • Related Report
      2017 Annual Research Report
    • Invited
  • [Presentation] ペリレンを光触媒とするオレフィン類のフルオロメチル化反応2017

    • Author(s)
      納戸直木・小池隆司・穐田宗隆
    • Organizer
      日本化学会 第97春季年会
    • Place of Presentation
      慶應義塾大学 日吉キャンパス
    • Year and Date
      2017-03-16
    • Related Report
      2016 Annual Research Report
  • [Presentation] Fine Design of Photoredox Systems for Catalytic Fluoromethylation2017

    • Author(s)
      Takashi Koike
    • Organizer
      日本化学会 第97春季年会 アジア国際シンポジウム
    • Place of Presentation
      慶應義塾大学 日吉キャンパス
    • Year and Date
      2017-03-16
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Diastereoserective Synthesis of Spiro Compounds Containing Fluoromethyl Group by Photoredox Catalysis2017

    • Author(s)
      Naoki Noto, Takashi Koike, Munetaka Akita
    • Organizer
      10th Workshop of Organic Chemistry for Junior Chemists (WOCJC10)
    • Place of Presentation
      Taipei, Taiwan
    • Year and Date
      2017-01-06
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research
  • [Presentation] ペリレンフォトレドックス触媒によるジフルオロメチル化反応2017

    • Author(s)
      納戸直木・小池隆司・穐田宗隆
    • Organizer
      第112回 有機合成シンポジウム
    • Related Report
      2017 Annual Research Report
  • [Presentation] 新規ジフルオロメチル化試薬を用いた光触媒的メタルフリージフルオロメチル化反応の開発2017

    • Author(s)
      納戸直木・小池隆司・穐田宗隆
    • Organizer
      第40回 フッ素化学討論会
    • Related Report
      2017 Annual Research Report
  • [Presentation] フォトレドックス触媒による酸素中心ラジカル発生を鍵とした芳香族化合物の直接的なアロイルオキシ化反応2017

    • Author(s)
      宮澤和己・小池隆司・穐田宗隆
    • Organizer
      第120回 触媒討論会
    • Related Report
      2017 Annual Research Report
  • [Presentation] Direct Aroyloxylation of Arenes with Aroyloxypyridinium Salts by Photoredox Catalysis2017

    • Author(s)
      Kazuki Miyazawa, Takashi Koike, Munetaka Akita
    • Organizer
      8th Pacific Symposium on Radical Chemistry (PSRC-8)
    • Related Report
      2017 Annual Research Report
  • [Presentation] Metal-Free Radical Difluoromethylation of Aromatic Alkenes Mediated by Visible Light-Induced Perylene Photoredox Catalysis2017

    • Author(s)
      Naoki Noto, Takashi Koike, Munetaka Akita
    • Organizer
      8th Pacific Symposium on Radical Chemistry (PSRC-8)
    • Related Report
      2017 Annual Research Report
  • [Presentation] フォトレドックス触媒作用を基盤とした芳香族化合物の直接ヘテロ官能基化2017

    • Author(s)
      小池隆司・宮澤和己・大地里佳・穐田宗隆
    • Organizer
      第41回 有機電子移動化学討論会
    • Related Report
      2017 Annual Research Report
  • [Presentation] Stereoselective Synthesis of Tetrasubstituted CF3-Alkenes via Photoredox-Catalyzed Sulfonyloxytrifluoromethylation of Internal Alkynes2016

    • Author(s)
      Ren Tomita, Takashi Koike, Munetaka Akita
    • Organizer
      The 11th International Conference on Cutting-Edge Organic Chemistry in Asia
    • Place of Presentation
      Daejeon, Korea
    • Year and Date
      2016-10-27
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Photoredox Catalysis: An Easy Access to Versatile Radical Functionalization2016

    • Author(s)
      Takashi Koike
    • Organizer
      2016 Pacific Rim Meeting on Electrochemical and Solid-State Science (PRiME 2016)
    • Place of Presentation
      Honolulu, Hawaii
    • Year and Date
      2016-10-02
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] フォトレドックス触媒を用いたフルオロメチル基含有スピロ化合物の合成2016

    • Author(s)
      納戸直木・小池隆司・穐田宗隆
    • Organizer
      第118回触媒討論会
    • Place of Presentation
      岩手大学
    • Year and Date
      2016-09-21
    • Related Report
      2016 Annual Research Report
  • [Presentation] Photoredox-Catalyzed Carbonyloxy-Trifluoromethylation of Allenes Leading to 2-CF3-Allyl Alcohol Derivatives2016

    • Author(s)
      Ren Tomita, Takashi Koike, Munetaka Akita
    • Organizer
      20th International Symposium on Homogeneous Catalysis (ISHCXX)
    • Place of Presentation
      Kyoto Terrsa
    • Year and Date
      2016-07-10
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Fluoromethylative Difunctionalization of Olefins by Photoredox Catalysis2016

    • Author(s)
      Takashi Koike, Yusuke Yasu, Ren Tomita, Munetaka Akita
    • Organizer
      1st International Symposium on Precisely Designed Catalysts with Customized Scaffolding
    • Place of Presentation
      Grand Front Osaka
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research / Invited
  • [Remarks] 研究室個人ホームページ

    • URL

      http://www.res.titech.ac.jp/~smart/A_koike01.html

    • Related Report
      2019 Annual Research Report
  • [Remarks] 研究室HP

    • URL

      http://www.res.titech.ac.jp/~smart/smartj.html

    • Related Report
      2018 Annual Research Report
  • [Remarks] 研究室ホームページ

    • URL

      http://www.res.titech.ac.jp/~smart/smartj.html

    • Related Report
      2017 Annual Research Report
  • [Remarks] 研究室HP

    • URL

      http://www.res.titech.ac.jp/~smart/A_koike01.html

    • Related Report
      2016 Annual Research Report
  • [Patent(Industrial Property Rights)] 高い還元力を有する芳香環光レドックス触媒2019

    • Inventor(s)
      小池隆司・納戸直木・谷口諒・高橋慶悟・穐田宗隆
    • Industrial Property Rights Holder
      小池隆司・納戸直木・谷口諒・高橋慶悟・穐田宗隆
    • Industrial Property Rights Type
      特許
    • Industrial Property Number
      2019-160380
    • Filing Date
      2019
    • Related Report
      2019 Annual Research Report
  • [Patent(Industrial Property Rights)] 多環芳香族炭化水素を光触媒とするフルオロメチル基含有化合物の製造方法2017

    • Inventor(s)
      小池隆司、納戸直木、穐田宗隆
    • Industrial Property Rights Holder
      小池隆司、納戸直木、穐田宗隆
    • Industrial Property Rights Type
      特許
    • Filing Date
      2017-02-20
    • Related Report
      2016 Annual Research Report

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Published: 2016-04-21   Modified: 2021-02-19  

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