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Cobalt-catalyzed C(sp3)-H functionalization and stereocontrol toward synthetic application

Research Project

Project/Area Number 19K16306
Research Category

Grant-in-Aid for Early-Career Scientists

Allocation TypeMulti-year Fund
Review Section Basic Section 47010:Pharmaceutical chemistry and drug development sciences-related
Research InstitutionHokkaido University

Principal Investigator

Tatsuhiko Yoshino  北海道大学, 薬学研究院, 准教授 (50756179)

Project Period (FY) 2019-04-01 – 2022-03-31
Project Status Completed (Fiscal Year 2021)
Budget Amount *help
¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000)
Fiscal Year 2020: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000)
Fiscal Year 2019: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000)
KeywordsC-H官能基化 / C-H活性化 / コバルト / ロジウム / イリジウム / 光酸化還元触媒 / コバルト触媒 / 光触媒 / 有機電解反応
Outline of Research at the Start

本研究ではコバルト触媒を用いたC(sp3)-H官能基化反応の発展を目指す。特にこれまで困難だった反応基質、反応剤との反応を実現し、有機合成的に使える反応の開発を目指す。そのために、(1)新しい配向基の開発および(2)近年急激に研究が進んできている光触媒・電気化学反応との融合を研究する。また研究代表者らが近年精力的に研究をおこなっているキラルカルボン酸やキラルアニオンとのハイブリッド触媒系とも融合させることで、不斉反応への展開も視野に入れて研究をおこなう

Outline of Final Research Achievements

We developed the allylation reactions of imines with simple alkenes and C-H allylation reactions directed by an imidate group using cobalt catalysts. We also developed new electron-deficient iridium catalysts bearing an electron deficient amide-pendant cyclopentadienyl ligand. Besides, we disclosed that the use of electron-deficient catalysts significantly accelerate C)sp3)-H bond cleavage.

Academic Significance and Societal Importance of the Research Achievements

有機化合物に広く存在する炭素-水素結合を直接活性化して反応させる手法は、合成化学的に非常に重要である。本研究では、特に反応が困難であるとされているC(sp3)-H結合の官能基化反応の開発へ向けた研究をおこない、コバルト、ロジウム、イリジウム触媒を用いた様々な反応を開発した。さらにC(sp3)-H結合の活性化を加速するための方向性を明らかとし、さらに新たな高反応性の触媒を新規に開発した。

Report

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

    (11 results)

All 2021 2020 2019

All Journal Article (9 results) (of which Int'l Joint Research: 1 results,  Peer Reviewed: 9 results,  Open Access: 4 results) Presentation (2 results)

  • [Journal Article] Chiral Carboxylic Acid Assisted Enantioselective C-H Activation with Achiral Cp<sup>x</sup>M<sup>III</sup> (M = Co, Rh, Ir) Catalysts2021

    • Author(s)
      Yoshino Tatsuhiko、Matsunaga Shigeki
    • Journal Title

      ACS Catalysis

      Volume: 11 Issue: 11 Pages: 6455-6466

    • DOI

      10.1021/acscatal.1c01351

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Development of Pseudo-C2-symmetric Chiral Binaphthyl Monocarboxylic Acids for Enantioselective C(sp3)-H Functionalization Reactions under Rh(III) Catalysis2021

    • Author(s)
      Kato Yoshimi、Lin Luqing、Kojima Masahiro、Yoshino Tatsuhiko、Matsunaga Shigeki
    • Journal Title

      ACS Catalysis

      Volume: 11 Issue: 7 Pages: 4271-4277

    • DOI

      10.1021/acscatal.1c00765

    • Related Report
      2020 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Iridium(III) Catalysts with an Amide-pendant Cyclopentadienyl Ligand: Double Aromatic Homologation Reactions of Benzamides via Fourfold C-H Activation2020

    • Author(s)
      Tomita Eiki、Yamada Kodai、Shibata Yu、Tanaka Ken、Kojima Masahiro、Yoshino Tatsuhiko、Matsunaga Shigeki
    • Journal Title

      Angewandte Chemie International Edition

      Volume: - Issue: 26 Pages: 10474-10478

    • DOI

      10.1002/anie.202003009

    • Related Report
      2020 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Rhodium(III)/Chiral Carboxylic Acid Catalyzed Enantioselective C(sp3)-H Alkylation of 8-Ethylquinolines with α,β-Unsaturated Carbonyl Compounds2020

    • Author(s)
      Huang Long-Tao、Fukagawa Seiya、Kojima Masahiro、Yoshino Tatsuhiko、Matsunaga Shigeki
    • Journal Title

      Organic Letters

      Volume: 22 Issue: 21 Pages: 8256-8260

    • DOI

      10.1021/acs.orglett.0c02872

    • Related Report
      2020 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Cp*CoIII/Chiral Carboxylic Acid‐Catalyzed Enantioselective 1,4‐Addition Reactions of Indoles to Maleimides2019

    • Author(s)
      Kurihara Takumaru、Kojima Masahiro、Yoshino Tatsuhiko、Matsunaga Shigeki
    • Journal Title

      Asian Journal of Organic Chemistry

      Volume: 9 Issue: 3 Pages: 368-371

    • DOI

      10.1002/ajoc.201900565

    • NAID

      120006896746

    • Related Report
      2019 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Catalytic Enantioselective Methylene C(sp3)-H Amidation of 8‐Alkylquinolines Using a Cp*RhIII /Chiral Carboxylic Acid System2019

    • Author(s)
      Fukagawa Seiya、Kojima Masahiro、Yoshino Tatsuhiko、Matsunaga Shigeki
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 58 Issue: 50 Pages: 18154-18158

    • DOI

      10.1002/anie.201911268

    • NAID

      120006890337

    • Related Report
      2019 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Imidate as the Intact Directing Group for the Cobalt-Catalyzed C-H Allylation2019

    • Author(s)
      Tanaka Ryo、Tanimoto Iku、Kojima Masahiro、Yoshino Tatsuhiko、Matsunaga Shigeki
    • Journal Title

      The Journal of Organic Chemistry

      Volume: 84 Issue: 20 Pages: 13203-13210

    • DOI

      10.1021/acs.joc.9b01972

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] Chiral 2-Aryl Ferrocene Carboxylic Acids for the Catalytic Asymmetric C(sp3)-H Activation of Thioamides2019

    • Author(s)
      Sekine Daichi、Ikeda Kazuki、Fukagawa Seiya、Kojima Masahiro、Yoshino Tatsuhiko、Matsunaga Shigeki
    • Journal Title

      Organometallics

      Volume: 38 Issue: 20 Pages: 3921-3926

    • DOI

      10.1021/acs.organomet.9b00407

    • NAID

      120006895040

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] Cobalt-catalyzed Synthesis of Homoallylic Amines from Imines and Terminal Alkenes2019

    • Author(s)
      Tanaka Ryo、Kojima Masahiro、Yoshino Tatsuhiko、Matsunaga Shigeki
    • Journal Title

      Chemistry Letters

      Volume: 48 Issue: 9 Pages: 1046-1049

    • DOI

      10.1246/cl.190378

    • NAID

      130007703028

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Presentation] 修飾 Cp イリジウム(III)錯体の合成及び 4 回の C-H 活性化を経るアントラセン誘導体合成反応の開発2020

    • Author(s)
      冨田永希、山田航大、柴田祐、田中健、小島正寛、吉野達彦、松永茂樹
    • Organizer
      第10回CSJ化学フェスタ2020
    • Related Report
      2020 Research-status Report
  • [Presentation] Asymmetric C-H functionalization reactions using Cp*Rh(III)/chiral disulfonate catalysts2020

    • Author(s)
      Tatsuhiko Yoshino, Shun Satake, Takumaru Kurihara, Junpei Hirose, Keisuke Nishikawa, Takuya Mochizuki, Manabu Hatano, Kazuaki Ishihara, Shigeki Matsunaga
    • Organizer
      第18回 次世代を担う有機化学シンポジウム
    • Related Report
      2020 Research-status Report

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

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