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長鎖ポリエーテル基により包み囲まれた遷移金属触媒中心による反応集積化

Publicly Offered Research

Project AreaOrganic Synthesis based on Integration of Chemical Reactions. New Methodologies and New Materials
Project/Area Number 22106517
Research Category

Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)

Allocation TypeSingle-year Grants
Review Section Science and Engineering
Research InstitutionKyoto University

Principal Investigator

辻 康之  京都大学, 工学研究科, 教授 (30144330)

Project Period (FY) 2010 – 2011
Project Status Completed (Fiscal Year 2011)
Budget Amount *help
¥7,020,000 (Direct Cost: ¥5,400,000、Indirect Cost: ¥1,620,000)
Fiscal Year 2011: ¥3,510,000 (Direct Cost: ¥2,700,000、Indirect Cost: ¥810,000)
Fiscal Year 2010: ¥3,510,000 (Direct Cost: ¥2,700,000、Indirect Cost: ¥810,000)
Keywords遷移金属触媒 / 長鎖ポリエーテル / 触媒活性 / 反応集積 / 触媒環境 / パラジウム触媒 / エチレングリコール / ホスフィン配位子 / 鈴木-宮浦カップリング / 塩化アリール / ONIOM計算
Research Abstract

本研究の目的は,高度に配位的に不飽和で,通常は極めて短寿命活性種である触媒中心を長鎖ポリエーテルで包み囲むことにより安定化し,かつ酸化的付加,金属交換,還元的脱離など一連の触媒素反応をその制御空間の中で高度に集積化し効率化することにより,極めて高活性,高選択的,高効率的な触媒反応を開発することにある。平成23年度においては,ポリエーテルの鎖長が,これまでに我々が開発した配位子と比較して約3倍に長い配位子を合成し,その鎖長伸張が集積化度に与える影響を検討した。昨年度と同様の塩化アリールを基質として用いたパラジウム触媒による鈴木-宮浦カップリング反応をモデル反応として検討を行った。その結果,長鎖ポリエーテルを導入した配位子が温和な条件で効率良く反応を進行させることが明らかになった。一方で,短い鎖を有する配位子を用いた触媒反応ではその反応効率が劇的に低下した.さらに,ホスフィン配位子以外のカルベン配位子を用いた反応集積化学も検討した.予備的知見ではあるが,長い鎖を導入したカルベン配位子を有するパラジウム触媒系では,塩化アリールを用いる鈴木-宮浦カップリング反応が室温で進行することを見出した。

Current Status of Research Progress
Current Status of Research Progress

2: Research has progressed on the whole more than it was originally planned.

Reason

本年度の研究は、交付申請書に記載した計画通り概ね順調に進行し、新しい配位子の開発とその触媒反応への応用に関する研究成果が得られたため.

Strategy for Future Research Activity

現在得られた成果は,既存の反応の効率を大きく改善する結果であった.今後は,長い鎖をもつ触媒系が高い活性を示した要因を明らかにすると共に,より挑戦的な課題として,新しい配位子よる新しい触媒反応の開発を進める必要があると考えている.

Report

(2 results)
  • 2011 Annual Research Report
  • 2010 Annual Research Report
  • Research Products

    (23 results)

All 2011 2010

All Journal Article (8 results) (of which Peer Reviewed: 8 results) Presentation (15 results)

  • [Journal Article] Palladium-Catalyzed Hydroesterification of Alkynes Employing Aryl Formates without the Use of External Carbon Monoxide2011

    • Author(s)
      Y.Katafuchi, T.Fujihara, T.Iwai I.Terao Y.Tsuji
    • Journal Title

      Adv.Synth.Catal.

      Volume: 353 Issue: 2-3 Pages: 475-482

    • DOI

      10.1002/adsc.201000750

    • Related Report
      2011 Annual Research Report 2010 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Copper-Catalyzed Hydrocarboxylation of Alkynes Using Carbon Dioxide and Hydrosilanes2011

    • Author(s)
      T.Fujihara, T.Xu, K.Semba, J.Terao, Y.Tsuji
    • Journal Title

      Angew.Chem.Int.Ed.

      Volume: 50 Issue: 2 Pages: 523-527

    • DOI

      10.1002/anie.201006292

    • Related Report
      2011 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Palladium(II) Complexes Bearing a Salicylaldiminato Ligand with Hydroxyl Group : Synthesis Structure Deprotonation and Catalysis2011

    • Author(s)
      Y.Murata, H.Ohgi, F.Fujihara, I.Terao, Y.Tsuji
    • Journal Title

      Inorg.Chim.Acta

      Volume: 368 Issue: 1 Pages: 237-241

    • DOI

      10.1016/j.ica.2010.12.036

    • Related Report
      2011 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis of a head-to-tail-type cyclodxtrin-based insulated molecular wire2011

    • Author(s)
      Terao, J, Ikai, K, Kambe, N, Seki, S, Saeki, A, Ohkoshi, K, Fujihara, T, Tsuji, Y
    • Journal Title

      CHEMICAL COMMUNICATIONS

      Volume: 47 Issue: 24 Pages: 6816-6818

    • DOI

      10.1039/c1cc12231b

    • Related Report
      2011 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Ruthenium-catalyzed Ring-closing Metathesis Accelerated by Long-range Steric Effect2011

    • Author(s)
      T.Fujihara, Y.Tomike, T.Ohtake I.Terao, Y.Tsuji
    • Journal Title

      Chem.Commun.

      Volume: 47 Issue: 34 Pages: 9699-9701

    • DOI

      10.1039/c1cc13304g

    • Related Report
      2011 Annual Research Report
    • Peer Reviewed
  • [Journal Article] 遷移金属錯体によるカルボニル官能基のアルキンへの付加反応2011

    • Author(s)
      辻康之、藤原哲晶
    • Journal Title

      有機合成化学協会誌

      Volume: 69 Pages: 1375-1388

    • NAID

      10030480503

    • Related Report
      2011 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Iridium-Catalyzed Annulation of N-Arylcarbamoyl Chlorides with Internal Alkynes2010

    • Author(s)
      T.Iwai, T.Fujihara, J.Terao, Y.Tsuji
    • Journal Title

      J.Am.Chem.Soc.

      Volume: 132 Pages: 9602-9603

    • Related Report
      2010 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Palladium-Catalyzed Intermolecular Addition of Formamides to Alkynes2010

    • Author(s)
      T.Fujihara, Y.Katafuchi, T.Iwai, J.Terao, Y.Tsuji
    • Journal Title

      J.Am.Chem.Soc.

      Volume: 132 Pages: 2094-2098

    • Related Report
      2010 Annual Research Report
    • Peer Reviewed
  • [Presentation] Hydrocarboxylat ion of Alkynes Employing Carbon Dioxide, Hydrosilanes, and Copper Catalysts2011

    • Author(s)
      Tetsuaki Fujihara, Tinguha Xu, Kazuhiko Semba, Jun Terao, Yasushi Tsuji
    • Organizer
      International Symposium on Catalysis and Fine Chemicals 2011 (C&FC2011)
    • Place of Presentation
      奈良(奈良県公会堂)
    • Year and Date
      2011-12-04
    • Related Report
      2011 Annual Research Report
  • [Presentation] Esterification of Aryl Halides Employing Aryl Formates and Palladium Catalysts2011

    • Author(s)
      Tomoya Hosoki, Yuko Katafuchi, Tomohiro Iwai, Tetsuaki Fujihara, Jun Terao, Yasushi Tsuji
    • Organizer
      International Symposium on Catalysis and Fine Chemicals 2011 (C&FC2011)
    • Place of Presentation
      奈良(奈良県公会堂)
    • Year and Date
      2011-12-04
    • Related Report
      2011 Annual Research Report
  • [Presentation] Carboxylation of Aryl Chlorides with CO2 Utilizing Nickel Catalysts2011

    • Author(s)
      Keisuke Nogi, Tinghua Xu, Tetsuaki Fujihara, Jun Terao, Yasushi Tsuji
    • Organizer
      International Symposium on Catalysis and Fine Chemicals 2011 (C&FC2011)
    • Place of Presentation
      奈良(奈良県公会堂)
    • Year and Date
      2011-12-04
    • Related Report
      2011 Annual Research Report
  • [Presentation] Functionalization via Metal Catalyzed Addition Reaction2011

    • Author(s)
      Yasushi Tsuji
    • Organizer
      C&FC2011 Pre-Symposium International Meeting on Recent Progress of Homogeneous and Heterogeneous Catalysts for Fine Chemical Synthesis
    • Place of Presentation
      京都(招待講演)
    • Year and Date
      2011-12-02
    • Related Report
      2011 Annual Research Report
  • [Presentation] ニッケル触媒によるアルキンへの二酸化炭素二分子導入反応の開発2011

    • Author(s)
      堀本裕一朗、徐庭華、藤原哲晶、寺尾潤、辻康之
    • Organizer
      石油学会関西支部第20回研究発表会
    • Place of Presentation
      京都(京都教育文化センター)
    • Year and Date
      2011-12-02
    • Related Report
      2011 Annual Research Report
  • [Presentation] 銅触媒存在下における二酸化炭素とシリルボランを用いたアルキンの官能基化2011

    • Author(s)
      谷洋介、仙波一彦、藤原哲晶、寺尾潤、辻康之
    • Organizer
      石油学会関西支部第20回研究発表会
    • Place of Presentation
      京都(京都教育文化センター)
    • Year and Date
      2011-12-02
    • Related Report
      2011 Annual Research Report
  • [Presentation] 遷移金属触媒を用いる高効率付加反応の開発2011

    • Author(s)
      辻康之
    • Organizer
      日本化学会東海支部地区講演会
    • Place of Presentation
      岐阜大学(招待講演)
    • Year and Date
      2011-11-26
    • Related Report
      2011 Annual Research Report
  • [Presentation] Ruthenium-catalyzed Ring-closing Metathesis Accelerated by Long-range Steric Effect2011

    • Author(s)
      Tetsuaki Fujihara, Yoshikazu Tomike, Toshiyuki Ohtake, Jun Terao, Yasushi Tsuji
    • Organizer
      The Seventh International Symposium on Integrated Synthesis (ISIS-7)
    • Place of Presentation
      神戸
    • Year and Date
      2011-10-09
    • Related Report
      2011 Annual Research Report
  • [Presentation] 銅触媒を用いた炭素-炭素多重結合の位置および立体選択的ヒドロホウ素化反広:異なる活性種による位置選択性の制御2011

    • Author(s)
      仙波一彦、四宮正暁、藤原哲晶、寺尾潤、辻康之
    • Organizer
      第58回有機金属化学討論会
    • Place of Presentation
      名古屋大学
    • Year and Date
      2011-09-08
    • Related Report
      2011 Annual Research Report
  • [Presentation] ギ酸アリールとパラジウム触媒を用いる芳香族ハロゲン化物のエステル化反応2011

    • Author(s)
      細木朋哉、片渕優子、岩井智弘、藤原哲晶、寺尾潤、辻康之
    • Organizer
      第58回有機金属化学討論会
    • Place of Presentation
      名古屋大学
    • Year and Date
      2011-09-08
    • Related Report
      2011 Annual Research Report
  • [Presentation] 二酸化炭素を用いたニッケル触媒による芳香族塩化物のカルボキシル化反応2011

    • Author(s)
      野木馨介、徐庭華、藤原哲晶、寺尾潤、辻康之
    • Organizer
      第58回有機金属化学討論会
    • Place of Presentation
      名古屋大学
    • Year and Date
      2011-09-08
    • Related Report
      2011 Annual Research Report
  • [Presentation] Transition Metal Catalyzed Addition of Carbonyl Functionality to C-C Multiple Bonds2011

    • Author(s)
      Yasushi Tsuji
    • Organizer
      14th Asian Chemical Congress 2011
    • Place of Presentation
      バンコク(タイ)(招待講演)
    • Year and Date
      2011-09-06
    • Related Report
      2011 Annual Research Report
  • [Presentation] Copper-Catalyzed Hydrocarboxylation of Alkynes Using Carbon Dioxide and Hydrosilanes2011

    • Author(s)
      Tetsuaki Fujihara, Tinghua Xu, Kazuhiko Semba, Jun Terao, Yasushi Tsuji
    • Organizer
      The 16th IUPAC International Symposium on Organometallic Chemistry Directed Towards Organic Synthesis (OMCOS-16)
    • Place of Presentation
      上海(中国)
    • Year and Date
      2011-07-25
    • Related Report
      2011 Annual Research Report
  • [Presentation] Copper-Catalyzed Highly Regio- and Stereoselective Hydroboration of Unsymmetrical Internal Alkynes : Control of Regioselectivity Using Different Active Species2011

    • Author(s)
      Kazuhiko Semba, Tetsuaki Fujihara, Jun Terao, Yasushi Tsuji
    • Organizer
      The 16th IUPAC International Symposium on Organometallic Chemistry Directed Towards Organic Synthesis (OMCOS-16)
    • Place of Presentation
      上海(中国)
    • Year and Date
      2011-07-25
    • Related Report
      2011 Annual Research Report
  • [Presentation] Transition-metal catalyzed addition of acid chlorides or formamides to alkynes2010

    • Author(s)
      Yasushi Tsuji
    • Organizer
      Pacifichem 2010
    • Place of Presentation
      Honolulu USA(招待講演)
    • Year and Date
      2010-12-18
    • Related Report
      2010 Annual Research Report

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Published: 2010-08-23   Modified: 2018-03-28  

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