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Development of carbon-silicon cross coupling reaction utilizing oxidative addition of chlorosilanes

Research Project

Project/Area Number 18K05115
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Review Section Basic Section 33020:Synthetic organic chemistry-related
Research InstitutionNational Institute of Advanced Industrial Science and Technology

Principal Investigator

Naganawa Yuki  国立研究開発法人産業技術総合研究所, 材料・化学領域, 主任研究員 (00613233)

Project Period (FY) 2018-04-01 – 2021-03-31
Project Status Completed (Fiscal Year 2020)
Budget Amount *help
¥4,420,000 (Direct Cost: ¥3,400,000、Indirect Cost: ¥1,020,000)
Fiscal Year 2020: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
Fiscal Year 2019: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
Fiscal Year 2018: ¥1,820,000 (Direct Cost: ¥1,400,000、Indirect Cost: ¥420,000)
Keywordsクロロシラン / クロスカップリング / ニッケル / パラジウム / 有機ケイ素 / 選択的合成 / アルミニウム / ルイス酸 / 酸化的付加 / 選択的 / 有機合成
Outline of Final Research Achievements

The Si-C bond formation reaction is a fundamental transformation to give useful organosilicon compounds which are widely used in synthetic chemistry and materials chemistry. In this study, we aim to develop a novel methodology for cleavage of Si-Cl bonds of chlorosilanes, which are classified as strong bonds. We realized the catalytic conversion of Si-Cl bonds to Si-C bonds by utilizing the cooperative activation with transition metal catalyst and Lewis acids. For example, we developed a nickel-catalyzed cross-coupling reaction between chlorosilanes and organoaluminum reagents. Furthermore, the use of palladium as a catalyst for the same reaction enabled us to obtain a wider range of substrate applications.

Academic Significance and Societal Importance of the Research Achievements

強固な結合の活性化と触媒的変換化学への挑戦は、近年有機化合物の持つ不活性なC-H結合やC-O結合などにおいて実践されているが、炭素の同族元素であるケイ素について本コンセプトを前面に打ち出した研究例は現在のところほとんど見られず、学術的意義があると考える。
有機ケイ素化合物の有用性は、合成化学や材料化学分野など幅広い分野ですでに十分に認識されており、本研究提案の実現により、これまで困難とされてきた有機ケイ素化合物の提供が可能となることで、それを基にした新奇な特性や応用技術の開発が期待されることから、優れた社会的意義が十分期待できる。

Report

(4 results)
  • 2020 Annual Research Report   Final Research Report ( PDF )
  • 2019 Research-status Report
  • 2018 Research-status Report
  • Research Products

    (13 results)

All 2021 2020 2019 2018 Other

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

  • [Journal Article] A General and Selective Synthesis of Methylmonochlorosilanes from Di-, Tri-, and Tetrachlorosilanes2020

    • Author(s)
      Naganawa Yuki、Sakamoto Kei、Nakajima Yumiko
    • Journal Title

      Organic Letters

      Volume: 23 Issue: 2 Pages: 601-606

    • DOI

      10.1021/acs.orglett.0c04175

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Hydrosilylation reactions of functionalized alkenes2020

    • Author(s)
      Y. Naganawa, K. Inomata, K. Sato, Y. Nakajima
    • Journal Title

      Tetrahedron Letters

      Volume: 61 Issue: 11 Pages: 151513-151513

    • DOI

      10.1016/j.tetlet.2019.151513

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] Nickel-Catalyzed Selective Cross-Coupling of Chlorosilanes with Organoaluminum Reagents2019

    • Author(s)
      Naganawa Yuki、Guo Haiqing、Sakamoto Kei、Nakajima Yumiko
    • Journal Title

      ChemCatChem

      Volume: 印刷中 Issue: 16 Pages: 3756-3759

    • DOI

      10.1002/cctc.201900047

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Presentation] パラジウム触媒を用いるジ、トリ、テトラクロロシランからのメチルモノクロロシランへの選択的変換反応2021

    • Author(s)
      永縄友規、坂本圭、中島裕美子
    • Organizer
      日本化学会第101春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] クロロシランの触媒的分子変換技術の開発2020

    • Author(s)
      永縄友規
    • Organizer
      令和元年度 産総研材料・化学シンポジウム
    • Related Report
      2019 Research-status Report
  • [Presentation] ニッケル触媒を用いるクロロシランの高効率触媒的分子変換2019

    • Author(s)
      永縄友規、郭海卿、坂本圭、中島裕美子
    • Organizer
      第8回JACI/GSCシンポジウム
    • Related Report
      2019 Research-status Report
  • [Presentation] Nickel-Catalyzed Selective Cross-Coupling of Chlorosilanes with Organoaluminum Reagents2019

    • Author(s)
      Yuki Naganawa, Haiqing Guo, Kei Sakamoto, Yumiko Nakajima
    • Organizer
      7th Asian Silicon Symposium
    • Related Report
      2019 Research-status Report
    • Int'l Joint Research
  • [Presentation] ケイ素化合物の活性化を駆使する触媒的有機合成2019

    • Author(s)
      永縄友規
    • Organizer
      有機合成化学協会関東支部 2019年度若手研究者のためのセミナー
    • Related Report
      2019 Research-status Report
    • Invited
  • [Presentation] ニッケル触媒によるクロロシラン類と有機アルミニウム試薬のクロスカップリング反応の開発2019

    • Author(s)
      永縄友規、郭海卿、坂本圭、中島裕美子
    • Organizer
      日本化学会第99春季年会
    • Related Report
      2018 Research-status Report
  • [Presentation] Catalytic Transformation of Chlorosilanes with Nickel Catalysts2018

    • Author(s)
      Yuki Naganawa, Teruo Beppu, Kazuhiro Matsumoto, Jiadi Huang, Haiqing Guo, Kazuhiko Sato, Shigeru Shimada, Yumiko Nakajima
    • Organizer
      9th European Silicon Days
    • Related Report
      2018 Research-status Report
    • Int'l Joint Research
  • [Presentation] クロロシラン類の酸化的付加を鍵とする触媒的分子変換2018

    • Author(s)
      永縄友規、別部輝生、松本和弘、郭海卿、佐藤一彦、中島裕美子
    • Organizer
      第65回有機金属化学討論会
    • Related Report
      2018 Research-status Report
  • [Book] クロスカップリング反応の有機ケイ素への新展開:ハロシランの酸化的付加を鍵とする触媒的分子変換2018

    • Author(s)
      永縄友規、中島裕美子
    • Total Pages
      2
    • Publisher
      化学同人
    • Related Report
      2018 Research-status Report
  • [Remarks] 産総研 触媒化学融合研究センター ケイ素化学チーム

    • URL

      https://irc3.aist.go.jp/incorporate/team/organosilicon-chemistry/

    • Related Report
      2020 Annual Research Report 2019 Research-status Report

URL: 

Published: 2018-04-23   Modified: 2022-01-27  

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