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Fine Tuning of Group 9 Metal-Chiral Acid Hybrid Catalysts Towards Deepening and Extension of Asymmetric C-H Functionalization

Research Project

Project/Area Number 20H02730
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Review Section Basic Section 33020:Synthetic organic chemistry-related
Research InstitutionHokkaido University

Principal Investigator

Matsunaga Shigeki  北海道大学, 薬学研究院, 客員教授 (50334339)

Co-Investigator(Kenkyū-buntansha) 吉野 達彦  北海道大学, 薬学研究院, 准教授 (50756179)
Project Period (FY) 2020-04-01 – 2023-03-31
Project Status Completed (Fiscal Year 2023)
Budget Amount *help
¥17,550,000 (Direct Cost: ¥13,500,000、Indirect Cost: ¥4,050,000)
Fiscal Year 2022: ¥5,590,000 (Direct Cost: ¥4,300,000、Indirect Cost: ¥1,290,000)
Fiscal Year 2021: ¥5,590,000 (Direct Cost: ¥4,300,000、Indirect Cost: ¥1,290,000)
Fiscal Year 2020: ¥6,370,000 (Direct Cost: ¥4,900,000、Indirect Cost: ¥1,470,000)
Keywords不斉触媒 / 不斉合成 / C-H活性化 / キラルカルボン酸 / 協働機能触媒 / キラル / C-H官能基化 / 遷移金属触媒 / キラル酸 / キラル塩基
Outline of Research at the Start

本研究計画では、アキラル第9族金属触媒+キラル酸触媒系の深化と適用範囲拡張を目指し、「不斉C-H官能基化における高度な立体制御と高い反応性の両立を実現する触媒設計コンセプトの確立」に挑む。3年間で3つの戦略、(i)アキラルCp部への官能基導入、(ii) キラル求核触媒との協働系、(iii) 新規キラル酸の活用、に取り組み、幅広いC-H官能基化反応に対し不斉化が実現可能なキラル触媒を創出する。

Outline of Final Research Achievements

In this study, we tried to expand the utility of our own hybridized catalysts of achiral group 9 metal CpM(III) catalysts and chiral acids. Conceptually new catalyst design to realize high stereoselectivity in asymmetric C-H functionalization was set as our research target. Three different catalyst design, (i) introduction of functional group into achiral Cp unit, (ii) cooperative system with chiral nucleophilic catalyst, and (iii) application of new chiral acids were successfully developed.

Academic Significance and Societal Importance of the Research Achievements

触媒的なC-H官能基化反応は、通常不活性なC-H結合を直接官能基化することが可能であり、反応工程数の削減や化学量論量の廃棄物の排出を防ぐことができるため、従来のクロスカップリング反応などと比較して、アトムエコノミーやステップエコノミーに優れた環境調和型な反応である。本研究の成果は、特にC-H官能基化における立体制御を自在に達成するための基盤となる新たなキラル触媒群の創出につながるものであり、特に医薬品等の持続可能性の高い生産に貢献するものである。

Report

(4 results)
  • 2023 Final Research Report ( PDF )
  • 2022 Annual Research Report
  • 2021 Annual Research Report
  • 2020 Annual Research Report
  • Research Products

    (18 results)

All 2023 2022 2021 2020 Other

All Int'l Joint Research (3 results) Journal Article (8 results) (of which Int'l Joint Research: 3 results,  Peer Reviewed: 8 results,  Open Access: 2 results) Presentation (5 results) (of which Invited: 1 results) Remarks (2 results)

  • [Int'l Joint Research] Dalian University of Technology(中国)

    • Related Report
      2021 Annual Research Report
  • [Int'l Joint Research] Qingdao University of Sci & Tech(中国)

    • Related Report
      2021 Annual Research Report
  • [Int'l Joint Research] Dalian University of Technology(中国)

    • Related Report
      2020 Annual Research Report
  • [Journal Article] Enantioselective Synthesis of 1,2‐Benzothiazine 1‐Imines via RuII/Chiral Carboxylic Acid‐Catalyzed C-H Alkylation/Cyclization2023

    • Author(s)
      Huang Long‐Tao、Kitakawa Yuta、Yamada Kodai、Kamiyama Futa、Kojima Masahiro、Yoshino Tatsuhiko、Matsunaga Shigeki
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 62 Issue: 29

    • DOI

      10.1002/anie.202305480

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Achiral Cp*Rh(III)/Chiral Lewis Base Cooperative Catalysis for Enantioselective Cyclization via C-H Activation2022

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

      Journal of the American Chemical Society

      Volume: - Issue: 16 Pages: 7058-7065

    • DOI

      10.1021/jacs.2c01223

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Ruthenium(II)/Chiral Carboxylic Acid Catalyzed Enantioselective C-H Functionalization of Sulfoximines2021

    • Author(s)
      Yoshino Tatsuhiko、Matsunaga Shigeki、Huang Long-Tao、Hirata Yuki、Kato Yoshimi、Lin Luqing、Kojima Masahiro
    • Journal Title

      Synthesis

      Volume: - Issue: 21 Pages: 4703-4710

    • DOI

      10.1055/a-1588-0072

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Cp*Ir(iii)/chiral carboxylic acid-catalyzed enantioselective C-H alkylation of ferrocene carboxamides with diazomalonates2021

    • Author(s)
      Mou Qi、Zhao Ruyuan、Niu Ruihan、Fukagawa Seiya、Shigeno Taiki、Yoshino Tatsuhiko、Matsunaga Shigeki、Sun Bo
    • Journal Title

      Organic Chemistry Frontiers

      Volume: 8 Issue: 24 Pages: 6923-6930

    • DOI

      10.1039/d1qo01344k

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Cp*Rh<sup>III</sup>/Chiral Disulfonate/CuOAc Catalyst System for the Enantioselective Intramolecular Oxyamination of Alkenes2021

    • Author(s)
      Hirose Jumpei、Wakikawa Takumi、Satake Shun、Kojima Masahiro、Hatano Manabu、Ishihara Kazuaki、Yoshino Tatsuhiko、Matsunaga Shigeki
    • Journal Title

      ACS Catalysis

      Volume: 11 Issue: 24 Pages: 15187-15193

    • DOI

      10.1021/acscatal.1c04699

    • 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
      2021 Annual Research Report 2020 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [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 Annual Research Report
    • Peer Reviewed / Open Access
  • [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 Annual Research Report
    • Peer Reviewed / Open Access
  • [Presentation] Cp*Co(III)触媒とキラルカルボン酸の組み合わせによるC-Hアミド化を経たチアジアジンの触媒的不斉合成2023

    • Author(s)
      平田裕己, 関根大地, 加藤佳美, Luqing Lin, 小島正寛, 吉野達彦, 松永茂樹
    • Organizer
      日本薬学会第143年会
    • Related Report
      2022 Annual Research Report
  • [Presentation] Catalyst Design for Asymmetric C-H Functionalization2022

    • Author(s)
      松永茂樹
    • Organizer
      白鷺セミナー
    • Related Report
      2022 Annual Research Report
  • [Presentation] Chiral acid/base-enabled achiral Rh(III)&Co(III)-catalyzed asymmetric C-H functionalization2022

    • Author(s)
      Shigeki Matsunaga
    • Organizer
      SYNTHESIS, WebCheminar on Asymmetric C-H Activation
    • Related Report
      2022 Annual Research Report
  • [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(オンライン開催)
    • Related Report
      2020 Annual Research Report
  • [Presentation] 不斉C-H結合官能基化を目指した新規キラル触媒の創製2020

    • Author(s)
      松永茂樹
    • Organizer
      有機合成化学協会Mukaiyama Award受賞講演会(オンライン開催)
    • Related Report
      2020 Annual Research Report
    • Invited
  • [Remarks] 薬品製造化学研究室

    • URL

      https://www.pharm.hokudai.ac.jp/yakuzou/publication.html

    • Related Report
      2021 Annual Research Report
  • [Remarks] 北海道大学大学院薬学研究院 薬品製造化学 発表論文

    • URL

      https://www.pharm.hokudai.ac.jp/yakuzou/publication.html

    • Related Report
      2020 Annual Research Report

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

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