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Development of HF capturing asymmetric phase-transfer catalysts using hydrofluoric acid and application

Research Project

Project/Area Number 17K14451
Research Category

Grant-in-Aid for Young Scientists (B)

Allocation TypeMulti-year Fund
Research Field Organic chemistry
Research InstitutionUniversity of the Ryukyus

Principal Investigator

Arimitsu Satoru  琉球大学, 理学部, 助教 (30546982)

Project Period (FY) 2017-04-01 – 2020-03-31
Project Status Completed (Fiscal Year 2019)
Budget Amount *help
¥4,550,000 (Direct Cost: ¥3,500,000、Indirect Cost: ¥1,050,000)
Fiscal Year 2019: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
Fiscal Year 2018: ¥1,040,000 (Direct Cost: ¥800,000、Indirect Cost: ¥240,000)
Fiscal Year 2017: ¥2,210,000 (Direct Cost: ¥1,700,000、Indirect Cost: ¥510,000)
Keywordsフッ素 / 有機触媒 / 不斉反応 / 有機分子触媒 / フッ化水素 / 相間移動触媒
Outline of Final Research Achievements

First, the synthetic route for the our designed urea catalysts was established as expected. However, it was revealed expanding the substrate scopes is very difficult with this methodology. Therefore, other types of catalysts bearing strong hydrogen bonding acceptor groups were searched, and we found N-oxide is promising candidate. The many types of chinchona-based N-oxide catalysts were prepared, and we analyzed its potential of association with HF by 19F NMR, and it revealed that chinchona-based N-oxide catalysts actually has the ability to associate with HF. Next, the substrate effects of catalysts are now examined and will be applied for the asymmetric fluorination.

Academic Significance and Societal Importance of the Research Achievements

本研究により、当初提案していたウレア触媒の合成を達成したものの、基質適応範囲の拡張が困難であることがわかった。しかし、同様のHF捕捉機能を持つNオキシドに着目し、シンコナルカロイド由来のNオキシド化合物の合成を達成し、実際にHFと会合することがわかった。本研究成果はHF水溶液を触媒反応に応用できる可能性を秘めており、今後引き続き触媒のデザインと反応開発を研究していく。

Report

(4 results)
  • 2019 Annual Research Report   Final Research Report ( PDF )
  • 2018 Research-status Report
  • 2017 Research-status Report
  • Research Products

    (17 results)

All 2020 2019 2018 2017

All Journal Article (6 results) (of which Peer Reviewed: 6 results,  Open Access: 1 results) Presentation (10 results) (of which Int'l Joint Research: 4 results,  Invited: 3 results) Book (1 results)

  • [Journal Article] Preparation of Enantiomerically Pure β,β-Diaryl β-Hydroxy-α-Amino Acids and Evaluation of Their Potential as Organocatalysts2020

    • Author(s)
      Satoru Arimitsu , Koki Oshiro , Katsuki Endo , Emi Gima , Samira Poorsadeghi
    • Journal Title

      Asian Journal of Organic Chemistry

      Volume: 9 Issue: 2 Pages: 238-241

    • DOI

      10.1002/ajoc.201900694

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Effects of Water Addition on a Catalytic Fluorination of Dienamine2019

    • Author(s)
      Kuraoku Daiki、Yonamine Tsunaki、Koja Genta、Yoshida Norio、Arimitsu Satoru、Higashi Masahiro
    • Journal Title

      Molecules

      Volume: 24 Issue: 19 Pages: 3428-3428

    • DOI

      10.3390/molecules24193428

    • NAID

      120006800746

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Stereoselective Synthesis of 4-Substituted 2, 4-Dichloro-2-butenals by α-and γ-Regioselective Double Chlorination of Dienamine Catalysis2018

    • Author(s)
      Satoru Arimitsu, Kazuto Terukina, Tatsuro Ishikawa
    • Journal Title

      Synlett

      Volume: 29 Issue: 14 Pages: 1887-1891

    • DOI

      10.1055/s-0037-1609559

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Journal Article] Diastereoselective synthesis of 5,5-disubstituted 3,3-difluorotetrahydrofurans2018

    • Author(s)
      Satoru Arimitsu, Makoto Nakasone and Emi Gima
    • Journal Title

      Tetrahedron Letters

      Volume: 59 Issue: 10 Pages: 887-890

    • DOI

      10.1016/j.tetlet.2018.01.053

    • Related Report
      2018 Research-status Report 2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] Cinchona-Based Primary Amine Catalyzed a Proximal Functionalization of Dienamines: Asymmetric α-Fluorination of α-Branched Enals2017

    • Author(s)
      Arimitsu Satoru、Yonamine Tsunaki、Higashi Masahiro
    • Journal Title

      ACS Catalysis

      Volume: 7 Issue: 7 Pages: 4736-4740

    • DOI

      10.1021/acscatal.7b01178

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] A new umpolung for direct γ-regioselective nucleophilic addition of alcohols to γ-enolizable α,β-unsaturated aldehydes2017

    • Author(s)
      Satoru Arimitsu, Mari Oshiro, Tsunaki Yonamine
    • Journal Title

      Tetrahedron Letters

      Volume: 58 Issue: 25 Pages: 2517-2520

    • DOI

      10.1016/j.tetlet.2017.05.058

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Presentation] ジアステレオ選択的γ,γ-二置換 α,α-ジフルオロ-γ-ブチロラクトン2020

    • Author(s)
      石川 達郎、有光 暁
    • Organizer
      第100回日本化学春年会
    • Related Report
      2019 Annual Research Report
  • [Presentation] 相間移動触媒によるβ-イノンエステルの不斉フッ素化反応2020

    • Author(s)
      岩佐 颯起、有光 暁
    • Organizer
      第100回日本化学春年会
    • Related Report
      2019 Annual Research Report
  • [Presentation] エノール化するα,β-不飽和アルデヒドの不斉αオキソ化反応2020

    • Author(s)
      儀間 恵美、有光 暁
    • Organizer
      第100回日本化学春年会
    • Related Report
      2019 Annual Research Report
  • [Presentation] Stereoselective fluorination of multi-substituted carbonyls with aminocatalysts2019

    • Author(s)
      Satoru Arimitsu
    • Organizer
      19th European Symposium on Fluorine Conference
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Cinchona-based primary amine catalyzed a proximal fluorination of dienamines: Importance of C-H hydrogen bonding for stereoselectivity2019

    • Author(s)
      Satoru Arimitsu
    • Organizer
      1st International Conference on Noncovalent Interaction
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Fluorination of dienamine catalysis and applicaitons2019

    • Author(s)
      Satoru Arimitsu
    • Organizer
      France-Japan Joint Forum on Organofluorine Chemistry for Future Pharmaceutical/Agricultural and Material Sciences
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] 高付加価値フッ化ビルディングブロックの創製と応用2019

    • Author(s)
      有光 暁
    • Organizer
      第9回フッ素若手の会
    • Related Report
      2019 Annual Research Report
    • Invited
  • [Presentation] Highly stereoselective fluorination of α-substituted β-diketones2019

    • Author(s)
      Samira Poorsadeghi, Katsuki Endo, Satoru Arimitsu
    • Organizer
      日本化学会 第99春季年会
    • Related Report
      2018 Research-status Report
    • Int'l Joint Research
  • [Presentation] 有機触媒による含フッ素合成素子の立体選択的合成とその応用2018

    • Author(s)
      儀間恵美、有光暁
    • Organizer
      第8回 フッ素化学若手の会
    • Related Report
      2018 Research-status Report
  • [Presentation] 有機触媒によるフッ素化アリル化合物の立体選択的合成法の開発2018

    • Author(s)
      石川達郎、有光暁
    • Organizer
      第8回 フッ素化学若手の会
    • Related Report
      2018 Research-status Report
  • [Book] Noncovalent Interactions in Catalysis: Chapter 2 Importance of C-H Hydrogen Bonding in Asymmetric Catalysis2019

    • Author(s)
      Satoru Arimitsu and Masahiro Higashi
    • Total Pages
      39
    • Publisher
      Royal Society of Chemistry
    • ISBN
      9781788014687
    • Related Report
      2018 Research-status Report

URL: 

Published: 2017-04-28   Modified: 2021-02-19  

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