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Developments and Applications of Alkyne Carbosilylation Using Trifluoromethylsilane

Research Project

Project/Area Number 17K14479
Research Category

Grant-in-Aid for Young Scientists (B)

Allocation TypeMulti-year Fund
Research Field Synthetic chemistry
Research InstitutionGunma University

Principal Investigator

Sugiishi Tsuyuka  群馬大学, 大学院理工学府, 助教 (30636220)

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 2018: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000)
Fiscal Year 2017: ¥2,470,000 (Direct Cost: ¥1,900,000、Indirect Cost: ¥570,000)
Keywordsカルボシリル化 / トリフルオロメチルシラン / 付加反応 / 遷移金属触媒 / アルキン / トリフルオロメチルアルケン
Outline of Final Research Achievements

In order to accomplish the alkyne carbosilylation using trifluoromethylsilane, the screening of the reaction conditions, such as the catalysts and the additives, and the substrates have been done. It appeared that the determining factor in this study is not only activation of the Carbon-Silicon bond but also acceleration of the addition of trifluoromethyl group to the alkynes. The role of trifluoromethylsilanes as the nucleophilic trifluoromethylation reagents and the electrophilic silylation reagents was evaluated during the screening using various alkynes.

Academic Significance and Societal Importance of the Research Achievements

実験室で容易に取り扱うことができ、かつ比較的安価であるトリフルオロメチルシランを用い、医薬、農薬、材料科学などにおいて必要とされているトリフルオロメチル化を、より原子効率よく短い合成経路で行える合成法の開発として、アルキンのカルボシリル化を目指した。その過程でハロアルケンの触媒的トリフルオロメチル化に成功した。本研究により、トリフルオロメチルシランの求核的トリフルオロメチル化剤および求電子的シリル化剤としての反応性が明らかになった。

Report

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

    (14 results)

All 2020 2019 2018 2017

All Journal Article (3 results) (of which Peer Reviewed: 3 results,  Open Access: 2 results,  Acknowledgement Compliant: 1 results) Presentation (11 results) (of which Int'l Joint Research: 1 results)

  • [Journal Article] Synthesis of 3-fluoro-2,5-disubstituted furans through ring expansion of gem-difluorocyclopropyl ketones2020

    • Author(s)
      Sugiishi Tsuyuka、Matsumura Chihori、Amii Hideki
    • Journal Title

      Organic & Biomolecular Chemistry

      Volume: 18 Issue: 18 Pages: 3459-3462

    • DOI

      10.1039/c9ob02713k

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Nucleophilic fluoroalkylation/cyclization route to fluorinated phthalides2018

    • Author(s)
      Inaba, M.; Sakai, Y.; Shinada, S.; Sugiishi, T.; Nishina, Y.; Shibata, N.; Amii, H.
    • Journal Title

      Beilstein J. Org. Chem.

      Volume: 14 Pages: 182-186

    • DOI

      10.3762/bjoc.14.12

    • Related Report
      2018 Research-status Report 2017 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] A Convenient Method for Catalytic Aromatic Pentafluoroethylation Using Potassium (Pentafluoroethyl)trimethoxyborate2017

    • Author(s)
      Tsuyuka Sugiishi, Daisuke Kawauchi, Mizuki Sato, Tatsuya Sakai, Hideki Amii
    • Journal Title

      Synthesis

      Volume: 49 Issue: 08 Pages: 1874-1878

    • DOI

      10.1055/s-0036-1589477

    • Related Report
      2017 Research-status Report
    • Peer Reviewed / Open Access / Acknowledgement Compliant
  • [Presentation] 求核的モノフルオロメチル合成ブロックの合成と反応2020

    • Author(s)
      芳賀 悠人, 田上 裕太, 杉石 露佳, 網井 秀樹
    • Organizer
      第100春季年会
    • Related Report
      2019 Annual Research Report
  • [Presentation] ペルフルオロアルキルリチウムの選択的発生と反応2020

    • Author(s)
      木檜 達哉, 渡部 鯨波, 杉石 露佳, 網井 秀樹
    • Organizer
      第100春季年会
    • Related Report
      2019 Annual Research Report
  • [Presentation] Difluorocyclopropanation of dehydroamino acid derivatives2020

    • Author(s)
      Ayari Sugiomi, Tsuyuka Sugiishi, Masayuki Kirihara, Hideki Amii
    • Organizer
      第100春季年会
    • Related Report
      2019 Annual Research Report
  • [Presentation] トリフルオロメチルアルキンを用いた含フッ素ピロールの合成2019

    • Author(s)
      海老沼明希, 杉石露佳, 網井秀樹
    • Organizer
      第42 回フッ素化学討論会
    • Related Report
      2019 Annual Research Report
  • [Presentation] 銅触媒を用いたハロアルケンのトリフルオロメチル化反応の開発2019

    • Author(s)
      岳思辰,小茂田和希,杉石露佳,網井秀樹
    • Organizer
      第42 回フッ素化学討論会
    • Related Report
      2019 Annual Research Report
  • [Presentation] 二種のアルキンを用いたトリフルオロメチルピロールの合成2019

    • Author(s)
      海老沼明希、杉石露佳、網井秀樹
    • Organizer
      第99日本化学会春季年会
    • Related Report
      2018 Research-status Report
  • [Presentation] 銅触媒を用いたハロアルケンのトリフルオロメチル化:基質適用範囲の調査2019

    • Author(s)
      岳思辰、小茂田和希、杉石露佳、網井秀樹
    • Organizer
      第99日本化学会春季年会
    • Related Report
      2018 Research-status Report
  • [Presentation] フタルイミジン誘導体合成を目指したトリフルオロメチル化反応2019

    • Author(s)
      今井佑哉、坂井達也、杉石露佳、網井秀樹
    • Organizer
      第99日本化学会春季年会
    • Related Report
      2018 Research-status Report
  • [Presentation] Synthesis of 3-Fluoro-2,5-disubstituted Furans from gem-Difluorocyclopropanes2018

    • Author(s)
      Tsuyuka Sugiishi, Chihori Matsumura, and Hideki Amii
    • Organizer
      2nd International symposium on Fluorine Chemistry
    • Related Report
      2018 Research-status Report
    • Int'l Joint Research
  • [Presentation] フッ素化シクロプロパンの環拡大反応による3-フルオロフランの合成2018

    • Author(s)
      松村千穂里、杉石露佳、網井秀樹
    • Organizer
      第76回 有機合成化学協会関東支部シンポジウム
    • Related Report
      2018 Research-status Report
  • [Presentation] フッ素化シクロプロパンの環拡大反応による3-フルオロフランの合成2018

    • Author(s)
      松村千穂里・杉石露佳・網井秀樹
    • Organizer
      日本化学会第98春季年会
    • Related Report
      2017 Research-status Report

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

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