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Copper(I)-Catalized Cross-Coupling of Organosilicon Compounds Utilizing Fluoride Ion Free Activators

Research Project

Project/Area Number 26410037
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Research Field Organic chemistry
Research InstitutionTokyo University of Agriculture and Technology

Principal Investigator

TSUBOUCHI Akira  東京農工大学, 工学(系)研究科(研究院), 助教 (40272637)

Project Period (FY) 2014-04-01 – 2017-03-31
Project Status Completed (Fiscal Year 2016)
Budget Amount *help
¥4,940,000 (Direct Cost: ¥3,800,000、Indirect Cost: ¥1,140,000)
Fiscal Year 2016: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
Fiscal Year 2015: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000)
Fiscal Year 2014: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000)
Keywordsクロスカップリング / ケイ素化合物 / 有機銅化合物 / 環状シリカート / 銅(I)アルコキシド / 触媒・化学プロセス / ジオール
Outline of Final Research Achievements

A fluoride-ion-free activation for the Si-C bond has been developed to achieve the copper(I) promoted cross-coupling of aryl- and alkenyldimethylsilanes with organic halides using a double activation of the silicon atom. In this activation, the formation of cyclic silicates by intramolecular coordination of copper alkoxide facilitates the transmetallation with copper(I) and simulteniously the coordination of the oxygen atom to the silicon atom activates the Si-C bond. Thus, we have found that fluoride-free cross-coupling of aryl- and alkenyldimethylsilanes with organic halides proceeded in the presence of monocopper(I) alkoxide of ethylene glycol. In addition, we have developed a copper(I) iodide/sodium hydride/ethylene glycol system as a new activator, which promoted the reaction of aryl- and alkenyldimethylsilanes with C(sp3)-X electrophiles bearing a beta-hydrogen to produce the cross- coupling products at ambient temperature within a short period of time.

Report

(4 results)
  • 2016 Annual Research Report   Final Research Report ( PDF )
  • 2015 Research-status Report
  • 2014 Research-status Report
  • Research Products

    (7 results)

All 2015 2014

All Journal Article (5 results) (of which Peer Reviewed: 5 results,  Acknowledgement Compliant: 5 results) Presentation (2 results)

  • [Journal Article] Cross-coupling between Aryl- and Alkenyldimethylsilanes and Organic Halides Promoted by a Copper(I) Iodide/Sodium Hydride/Ethylene Glycol System2015

    • Author(s)
      Takeshi Takeda, Yuichiro Takeda, Akira Tsubouchi
    • Journal Title

      Chem. Lett.

      Volume: 44 Issue: 6 Pages: 809-811

    • DOI

      10.1246/cl.150171

    • NAID

      130005074584

    • Related Report
      2015 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Diversity Oriented Synthesis of Conjugate Dienes and AlkenylCyclopropanes Utilizing Silyl Group-substituted Titanium Carbene Complexes as Bimetallic Synthetic Reagents2014

    • Author(s)
      Takeshi Takeda, Ayako Mori, Tomoya. Fujii, Akira Tsubouchi
    • Journal Title

      Tetrahedron

      Volume: 70 Issue: 35 Pages: 5776-5786

    • DOI

      10.1016/j.tet.2014.06.043

    • Related Report
      2014 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Copper(I)-Promoted Alkylation of Alkenylbenzyldimethylsilanes2014

    • Author(s)
      Takeshi Takeda, Ryo Matsumura, Hideki Wasa, Akira Tsubouchi
    • Journal Title

      Asian J. Org. Chem.

      Volume: 3 Issue: 8 Pages: 838-841

    • DOI

      10.1002/ajoc.201402060

    • Related Report
      2014 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Copper(i) 2-Hydroxyethoxide-promoted Cross-coupling of Aryl- and Alkenyldimethylsilanes with Organic Halides2014

    • Author(s)
      Takeshi Takeda, Ryosuke Obata, Daisuke Muramatsu, Yuichiro Takeda, Akira Tsubouchi
    • Journal Title

      Chem. Commun.

      Volume: 50 Issue: 96 Pages: 15156-15158

    • DOI

      10.1039/c4cc07371a

    • Related Report
      2014 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Diversity-Oriented Stereoselective Synthesis of β,γ-Disubstituted tert -Homoallylic Alcohols2014

    • Author(s)
      Takeshi Takeda, Sota Amarume, Ippei Sekioka, Akira Tsubouchi
    • Journal Title

      Org. Lett.

      Volume: 17 Issue: 5 Pages: 1150-1153

    • DOI

      10.1021/acs.orglett.5b00084

    • Related Report
      2014 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Presentation] 不飽和チタンーカルベン錯体とビニルボラン及びビニルシランの反応2015

    • Author(s)
      武田 猛、寺元佑蔵、井上雄太、坪内 彰、
    • Organizer
      日本化学会第95春季年会
    • Place of Presentation
      日本大学船橋キャンパス(千葉)
    • Year and Date
      2015-03-26 – 2015-03-29
    • Related Report
      2014 Research-status Report
  • [Presentation] ヨウ化銅(I)ー水素化ナトリウムーエチレングリコール系により促進されるアリールおよびアルケニルシランのクロスカップリング2015

    • Author(s)
      武田 猛、武田有一郎、坪内 彰
    • Organizer
      日本化学会第95春季年会
    • Place of Presentation
      日本大学船橋キャンパス(千葉)
    • Year and Date
      2015-03-26 – 2015-03-29
    • Related Report
      2014 Research-status Report

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Published: 2014-04-04   Modified: 2018-03-22  

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