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The enantio-switching of five continuous chiral centers

Research Project

Project/Area Number 19K22178
Research Category

Grant-in-Aid for Challenging Research (Exploratory)

Allocation TypeMulti-year Fund
Review Section Medium-sized Section 33:Organic chemistry and related fields
Research InstitutionTohoku University

Principal Investigator

Hayashi Yujiro  東北大学, 理学研究科, 教授 (00198863)

Project Period (FY) 2019-06-28 – 2022-03-31
Project Status Completed (Fiscal Year 2021)
Budget Amount *help
¥6,500,000 (Direct Cost: ¥5,000,000、Indirect Cost: ¥1,500,000)
Fiscal Year 2020: ¥2,600,000 (Direct Cost: ¥2,000,000、Indirect Cost: ¥600,000)
Fiscal Year 2019: ¥3,900,000 (Direct Cost: ¥3,000,000、Indirect Cost: ¥900,000)
Keywords不斉合成 / 有機触媒 / ドミノ反応 / エナンチオスイッチング / 鏡像異性体 / エナンチオ・ダイバージェント / キラル合成 / 不斉触媒反応 / キラリティー
Outline of Research at the Start

単一の絶対立体配置を有する触媒を用いて、分子の両対掌体をそれぞれ高選択的に合成するエナンチオスイッチングという現象の多くは、有機金属化合物を触媒に用いた反応である。アキラルな添加剤がキラルな金属触媒に配位し、活性部位が変化し、エナンチオ選択性が逆転すると説明される。4つまでの立体中心の反転例は知られているが、5つ以上の立体中心の反転例は知られていない。また、そのような現象が起こりうる反応系を設計する事も、現在の有機化学の知識では困難である。ステロイド誘導体の合成検討中、偶然にも連続する5つの不斉中心のエナンチオスイッチングが起こるという萌芽的知見を見出したが、本研究ではその原理を明らかにする。

Outline of Final Research Achievements

We have found an enantioswitching phenomenon in the synthesis of steroid intermediate. Both enantiomers are produced in high optical yields by using the same asymmetric organocatalyst, changing the reaction solvent and the amount of water. Furthermore, we also observed an enantiodivergent phenomenon. We synthesized the central chiral molecules by the organocatalyst mediated reactions. During the transfer of the central chirality to the axial chirality, both atropisomers were obtained with excellent enantioselectivity.

Academic Significance and Societal Importance of the Research Achievements

キラルな光学活性化合物を得る優れた手法の一つが不斉触媒反応である。鏡像異性体を合成する時は、逆の絶対配置を有する触媒を用いるのが常識である。これに対し、希少な例ではあるが反応条件を変化させることで、同じ鏡像異性体を触媒として用いても、反対の鏡像異性体が得られる現象(エナンチオスイッチング)が知られている。光学活性化合物には、他方の鏡像異性体の入手が困難な化合物も多い。同一の絶対立体配置を有する化合物が不斉触媒として作用し、両鏡像異性体を高い光学純度で得ることができれば、学術的、社会的な意義が大きい。今回、このような触媒および反応を見出した。

Report

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

    (9 results)

All 2021 2020

All Journal Article (1 results) (of which Peer Reviewed: 1 results) Presentation (8 results) (of which Int'l Joint Research: 5 results,  Invited: 6 results)

  • [Journal Article] Enantiodivergent One‐Pot Synthesis of Axially Chiral Biaryls Using Organocatalyst‐Mediated Enantioselective Domino Reaction and Central‐to‐Axial Chirality Conversion2021

    • Author(s)
      Koshino Seitaro、Taniguchi Tohru、Monde Kenji、Kwon Eunsang、Hayashi Yujiro
    • Journal Title

      Chemistry A European Journal

      Volume: 27 Issue: 63 Pages: 15786-15794

    • DOI

      10.1002/chem.202102797

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Presentation] One-pot enantiodivergent synthesis of axially chiral biaryls using organocatalyst2021

    • Author(s)
      Seitaro Koshino, Tohru Taniguchi, Kenji Monde, Eunsang Kwon, Yujiro Hayashi
    • Organizer
      日本化学会第101春季年会
    • Related Report
      2021 Annual Research Report
  • [Presentation] Pot Economy in Total Synthesis2021

    • Author(s)
      Yuiro Hayashi
    • Organizer
      World Class Professor 2021, (on line) Universitas Gadjah Mada, Indonesia and Institut des Sciences Moleculaires de Marseille
    • Related Report
      2021 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Recent development of asymmetric catalytic reactions using diphenylprolinol silyl ether as a catalyst2021

    • Author(s)
      Yuiro Hayashi
    • Organizer
      2021 International Chemical Congress of Pacific Basin Societies (PACIFICHEM 2021)
    • Related Report
      2021 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Time and pot economical synthesis of biologically active molecules using organocatalyst2021

    • Author(s)
      Yuiro Hayashi
    • Organizer
      2021 International Chemical Congress of Pacific Basin Societies (PACIFICHEM 2021)
    • Related Report
      2021 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] One-pot enantiodivergent synthesis of axially chiral biaryls using organocatalyst2021

    • Author(s)
      Seitaro Koshino, Tohru Taniguchi, Kenji Monde, Eunsang Kwon, Yujiro Hayashi
    • Organizer
      日本化学会第101春季年会、オンライン開催
    • Related Report
      2020 Research-status Report
  • [Presentation] 実用的有機触媒反応の開発および生物活性化合物の短工程合成への展開2021

    • Author(s)
      林 雄二郎
    • Organizer
      第62回有機合成化学協会 協会賞受賞講演、有機合成化学協会、如水会館、東京
    • Related Report
      2020 Research-status Report
    • Invited
  • [Presentation] Time and Pot Economy in Total Synthesis2021

    • Author(s)
      Yujiro Hayashi
    • Organizer
      2021 8th International Conference on Chemical and Biological Sciences (ICCBS 2021), 2021 11th International Conference on Chemistry and Chemical Process (ICCCP 2021)
    • Related Report
      2020 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] Time Economy in Total Synthesis2020

    • Author(s)
      Yujiro Hayashi
    • Organizer
      57th Annual Convertion of Chemists (ACC), Indian Chemical Society (ICS), Organic & Bio-Chemistry Section, IISER Kolkata, India (on line) (plenary)
    • Related Report
      2020 Research-status Report
    • Int'l Joint Research / Invited

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Published: 2019-07-04   Modified: 2023-01-30  

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