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Control of transition state in metal-supported-catalyzed reactions with organo catalysis

Research Project

Project/Area Number 15KT0066
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeMulti-year Fund
Section特設分野
Research Field Transition State Control
Research InstitutionKyushu University

Principal Investigator

Kuwano Ryoichi  九州大学, 理学研究院, 教授 (20273477)

Project Period (FY) 2015-07-10 – 2020-03-31
Project Status Completed (Fiscal Year 2019)
Budget Amount *help
¥18,070,000 (Direct Cost: ¥13,900,000、Indirect Cost: ¥4,170,000)
Fiscal Year 2019: ¥3,510,000 (Direct Cost: ¥2,700,000、Indirect Cost: ¥810,000)
Fiscal Year 2018: ¥3,640,000 (Direct Cost: ¥2,800,000、Indirect Cost: ¥840,000)
Fiscal Year 2017: ¥3,640,000 (Direct Cost: ¥2,800,000、Indirect Cost: ¥840,000)
Fiscal Year 2016: ¥3,640,000 (Direct Cost: ¥2,800,000、Indirect Cost: ¥840,000)
Fiscal Year 2015: ¥3,640,000 (Direct Cost: ¥2,800,000、Indirect Cost: ¥840,000)
Keywords不斉合成 / 金属担持触媒 / 有機触媒 / 水素化 / キノリン / イミン / 光学活性アミン / 触媒的不斉合成 / ブレンステッド酸 / アミン / 金属微粒子触媒 / 選択性制御 / テトラヒドロキノリン / 不斉水素化 / ロジウム / ルテニウム / 芳香族複素環 / 金属錯体触媒 / 不斉触媒 / 合成化学 / 触媒・化学プロセス / 有機工業化学 / 立体化学制御
Outline of Final Research Achievements

We have designed a new catalyst system constituted of optically active Broensted acid and metal-supported catalyst, in which each catalyst activates the substrate and molecular hydrogen. Furthermore, the catalyst system has been applied to the asymmetric hydrogenation of quinolines and imines.
The hydrogenation of 2-phenylquinoline was attempted with various combinations of the Broensted acid and metal-supported catalyst. We found that chiral BINOL-based phosphoric acid or sulfonimide allows the hydrogenation to proceed with a moderate enantioselectivity. In particular, the chiral binaphthyl-based sulfonimide bearing 3,5-di(tert-butyl)phenyl groups at its 3,3'-positions exhibited the highest enantioselectivity, giving the desired product with 36% ee.

Academic Significance and Societal Importance of the Research Achievements

一般に、触媒的不斉反応は光学活性金属錯体、塩基性窒素化合物、ブレンステッド酸の単一の分子を用いて行われる。また、これらの可溶性分子を2種類組み合わせた触媒システムによる不斉反応もいくつか知られている。一方、金属担持触媒は有機反応の触媒としてしばしば利用されるが、その高度な立体化学的な遷移状態制御が困難であると考えられる。
本研究では、金属担持触媒と光学活性ブレンステッド酸による立体化学制御を組み合わせることによって、金属担持触媒反応における立体化学制御の実現を目指すものであり、本研究成果によってその実現可能性が示された。

Report

(6 results)
  • 2019 Annual Research Report   Final Research Report ( PDF )
  • 2018 Research-status Report
  • 2017 Research-status Report
  • 2016 Research-status Report
  • 2015 Research-status Report
  • Research Products

    (28 results)

All 2020 2019 2018 2017 2016 2015

All Journal Article (6 results) (of which Int'l Joint Research: 1 results,  Peer Reviewed: 6 results,  Open Access: 1 results,  Acknowledgement Compliant: 2 results) Presentation (22 results) (of which Int'l Joint Research: 16 results,  Invited: 9 results)

  • [Journal Article] Room-Temperature Benzylic Alkylation of Benzylic Carbonates: Improvement of Palladium Catalyst and Mechanistic Study2019

    • Author(s)
      Kuwano Ryoichi、Yokogi Masashi、Sakai Ken、Masaoka Shigeyuki、Miura Takashi、Won Sungyong
    • Journal Title

      Organic Process Research & Development

      Volume: 23 Issue: 8 Pages: 1568-1579

    • DOI

      10.1021/acs.oprd.9b00210

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Ruthenium-Catalyzed Chemo- and Enantioselective Hydrogenation of Isoquinoline Carbocycles2018

    • Author(s)
      Jin Yushu、Makida Yusuke、Uchida Tatsuya、Kuwano Ryoichi
    • Journal Title

      The Journal of Organic Chemistry

      Volume: 83 Issue: 7 Pages: 3829-3839

    • DOI

      10.1021/acs.joc.8b00190

    • Related Report
      2018 Research-status Report 2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] Palladium-Catalyzed Decarboxylation of Benzyl Fluorobenzoates2017

    • Author(s)
      Kuwano Ryoichi、Makida Yusuke、Matsumoto Yasutaka
    • Journal Title

      Synlett

      Volume: 28 Issue: 19 Pages: 2573-2576

    • DOI

      10.1055/s-0036-1588572

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] Palladium-catalyzed Benzylic Substitution of Benzyl Carbonates with Phosphorus Nucleophiles2017

    • Author(s)
      Makida Yusuke、Usui Kazumi、Ueno Satoshi、Kuwano Ryoichi
    • Journal Title

      Chemistry Letters

      Volume: 46 Issue: 12 Pages: 1814-1817

    • DOI

      10.1246/cl.170901

    • NAID

      130006243148

    • Related Report
      2017 Research-status Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Asymmetric Hydrogenation of Isoxazolium Triflates with a Chiral Iridium Catalyst2016

    • Author(s)
      Rhuhei Ikeda and Rhoichi Kuwano
    • Journal Title

      Chemistry A European Journal

      Volume: 22 Issue: 25 Pages: 8610-8618

    • DOI

      10.1002/chem.201600732

    • Related Report
      2016 Research-status Report 2015 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Asymmetric Hydrogenation of Azaindoles: Chemo‐ and Enantioselective Reduction of Fused Aromatic Ring Systems Consisting of Two Heteroarenes2016

    • Author(s)
      Yusuke Makida, Masahiro Saita, Takahiro Kuramoto, Kentaro Ishizuka, Ryoichi Kuwano
    • Journal Title

      Angew. Chem. Int. Ed.

      Volume: 55 Issue: 39 Pages: 11859-11862

    • DOI

      10.1002/anie.201606083

    • Related Report
      2016 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Presentation] Kinetic Resolution of Axially Chiral 1-Arylnaphthalenes through the Arene Hydrogenation with Chiral Ruthenium Catalyst2020

    • Author(s)
      WON Sungyong, JIN Yushu, KUWANO Ryoichi
    • Organizer
      日本化学会第100春季年会
    • Related Report
      2019 Annual Research Report
  • [Presentation] Switching Chemoselectivity in Asymmetric Hydrogenation of Azaindoles2019

    • Author(s)
      Kuwano Ryoichi
    • Organizer
      International Congress on Pure & Applied Chemistry Yangon 2019
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Asymmetric Hydrogenation of Pyridine Ring in Azaindoles by Chiral Iridium Catalyst2019

    • Author(s)
      張奥、中山裕棋、槇田祐輔、桑野良一
    • Organizer
      第124回触媒討論会
    • Related Report
      2019 Annual Research Report
  • [Presentation] Enantioselective Hydrogenation of Carbocyclic Arenes with Asymmetric Catalysis2019

    • Author(s)
      Kuwano Ryoichi
    • Organizer
      The 18th Asian Chemical Congress
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] イリジウム触媒によるアザインドールのピリジン環選択的な不斉水素化2019

    • Author(s)
      中山裕棋、槇田祐輔、桑野良一
    • Organizer
      日本化学会 第99春季年会
    • Related Report
      2018 Research-status Report
  • [Presentation] Hydrogenation of Heterocyclic and Carbocyclic Arenes with Asymmetric Catalysis2018

    • Author(s)
      桑野良一
    • Organizer
      The International Symposium on Frontiers in Catalytic Chemistry
    • Related Report
      2018 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] Chemo- and Enantioselective Hydrogenation of Quinoline and Isoquinoline Carbocycles2018

    • Author(s)
      槇田祐輔、金玉樹、池田龍平、桑野良一
    • Organizer
      28th International Conference on Organometallic Chemistry
    • Related Report
      2018 Research-status Report
    • Int'l Joint Research
  • [Presentation] アザインドールの触媒的不斉水素化における化学選択性2018

    • Author(s)
      中山裕棋、槇田祐輔、桑野良一
    • Organizer
      第65回有機金属化学討論会
    • Related Report
      2018 Research-status Report
  • [Presentation] アザインドールの触媒的不斉水素化における化学選択性2018

    • Author(s)
      槇田祐輔、中山裕棋、桑野良一
    • Organizer
      第122回触媒討論会
    • Related Report
      2018 Research-status Report
  • [Presentation] Switchable Chemoselectivity in Asymmetric Hydrogenation of Azaindoles2018

    • Author(s)
      槇田祐輔、中山裕棋、桑野良一
    • Organizer
      第14回国際有機化学京都会議
    • Related Report
      2018 Research-status Report
    • Int'l Joint Research
  • [Presentation] Control of Chemoselectivity in Enantioselective Hydrogenation of Azaindoles with Chiral Metal Complexes2018

    • Author(s)
      桑野良一
    • Organizer
      13th The International Symposium on Organic Reactions
    • Related Report
      2018 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] Control of Chemoselectivity in Asymmetric Hydrogenation of Fused Heteroarenes2018

    • Author(s)
      桑野良一
    • Organizer
      6th Japan-UK Symposium on Asymmetric Catalysis
    • Related Report
      2018 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] Iridium-Catalyzed Asymmetric Hydrogenation of Pyridine Rings of Azaindoles2018

    • Author(s)
      中山裕棋、槇田祐輔、桑野良一
    • Organizer
      6th Japan-UK Symposium on Asymmetric Catalysis
    • Related Report
      2018 Research-status Report
    • Int'l Joint Research
  • [Presentation] Enantioselective Hydrogenation of Quinolines and Isoquinoline Carbocycles2018

    • Author(s)
      Ryoichi Kuwano, Yushu Jin, Ryuhei Ikeda, Kazuki Hirasada, Yusuke Makida
    • Organizer
      IRCCS-JST CREST Joint Symposium
    • Related Report
      2017 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] Asymmetric Hydrogenation of Heteroarenes2017

    • Author(s)
      Ryoichi Kuwano
    • Organizer
      ISPAC 2017
    • Related Report
      2017 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] Enantioselective Hydrogenation of Nitrogen-Containing Heteroarenes2017

    • Author(s)
      Ryoichi Kuwano
    • Organizer
      OMCOS 19
    • Related Report
      2017 Research-status Report
    • Int'l Joint Research
  • [Presentation] Chemoselective and Enantioselective Hydrogenation of Quinoline and Isoquinoline Carbocycles2017

    • Author(s)
      Ryoichi Kuwano, Yushu Jin, Ryuhei Ikeda, Kazuki Hirasada, Yusuke Makida
    • Organizer
      ICCEOCA-12 and ARNCEOCA 3
    • Related Report
      2017 Research-status Report
    • Int'l Joint Research
  • [Presentation] Enantioselective Hydrogenation of Carbocyclic Arenes2016

    • Author(s)
      Ryoichi Kuwano, Ryuhei Ikeda, Yusuke Makida
    • Organizer
      IKCOC-13
    • Place of Presentation
      京都
    • Year and Date
      2016-11-12
    • Related Report
      2015 Research-status Report
    • Int'l Joint Research
  • [Presentation] Enantioselective Hydrogenation of Heteroarenes and Arenes2016

    • Author(s)
      Ryoichi Kuwano
    • Organizer
      5th UK-Japanese Symposium on Asymmetric Catalysis
    • Place of Presentation
      Manchester
    • Year and Date
      2016-03-14
    • Related Report
      2015 Research-status Report
    • Invited
  • [Presentation] Enantioselective Hydrogenation of Heterocyclic Arenes2016

    • Author(s)
      Ryoichi Kuwano
    • Organizer
      ISPAC 2016
    • Place of Presentation
      マレーシア、クチン
    • Related Report
      2016 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] Chemo- and Enantioselective Hydrogenation of Azaindoles2016

    • Author(s)
      Ryoichi Kuwano, Masahiro Saita, Yusuke Makida
    • Organizer
      C&FC 2016
    • Place of Presentation
      台北、台湾
    • Related Report
      2016 Research-status Report
    • Int'l Joint Research
  • [Presentation] Catalytic asymmetric hydrogenation of carbocyclic arenes2015

    • Author(s)
      Ryoichi Kuwano
    • Organizer
      Pacifichem 2015
    • Place of Presentation
      Honolulu
    • Year and Date
      2015-12-16
    • Related Report
      2015 Research-status Report
    • Int'l Joint Research

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Published: 2015-07-14   Modified: 2022-11-04  

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