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新規機能性金属錯体マテリアルの創出とキノリン・インドールライブラリー構築への展開

Research Project

Project/Area Number 14657559
Research Category

Grant-in-Aid for Exploratory Research

Allocation TypeSingle-year Grants
Research Field Chemical pharmacy
Research InstitutionNational Institute for Materials Science

Principal Investigator

下田 正彦 (2003-2004)  独立行政法人物質・材料研究機構, 材料研究所, 主席研究員 (60343836)

塚本 史郎 (2002)  独立行政法人物質・材料研究機構, ナノマテリアル研究所, 主任研究員 (50344453)

Co-Investigator(Kenkyū-buntansha) 西田 篤司  国立大学法人千葉大学, 大学院・薬学研究院, 教授 (80130029)
有澤 光弘  国立大学法人千葉大学, 大学院・薬学研究院, 助手 (40312962)
下田 正彦  独立行政法人物質・材料研究機構, 材料研究所, 主席研究員 (60343836)
Project Period (FY) 2002 – 2004
Project Status Completed (Fiscal Year 2004)
Budget Amount *help
¥3,000,000 (Direct Cost: ¥3,000,000)
Fiscal Year 2004: ¥1,200,000 (Direct Cost: ¥1,200,000)
Fiscal Year 2003: ¥900,000 (Direct Cost: ¥900,000)
Fiscal Year 2002: ¥900,000 (Direct Cost: ¥900,000)
Keywords触媒 / 有機金属錯体 / ガリウム砒素単結晶 / 分子線エピタキシー / 硫黄 / 炭素-炭素結合 / テトラキストリフェニルフォスフィンパラジウム / 複素環 / 分子線エピタキシィ / GaAs / ルテニウム
Research Abstract

創薬化学・有機合成化学で重要な有機金属錯体触媒の固定に関する研究を行っている。すなわち、従来溶液として用いられる有機金属錯体を、基板(半導体、金属、絶縁体)表面上に固定することで、より安定で、再利用可能な新素材の開発を試みている。また、ルテニウム触媒を用いる置換キノリン及びインドールの新しい合成法の開発し、これらのライブラリー構築を行っている。
昨年度までの研究で、硫黄原子の(2x6)構造をもつGaAs単結晶基板に固定された有機Pd錯体Pd(PPh_3)_4)が、Heck反応、鈴木カップリング等の有機反応において、極めて高い触媒活性を有する事を見出した。さらに、硫黄処理を真空蒸着法から多硫化アンモニウム水溶液処理に代えることで、効率、安定性ともに大幅に改善されることが判った。また、ルテニウム触媒を用いる閉環メタセシスにより置換キノリン及びインドールの新しい合成法、ハロアミネーションを用いる置換インドールの新しい合成法の開発に成功した。
今年度は、この半導体上に固定された金属錯体の触媒活性の向上を目指し、処理条件等による活性の違いを調べた。また、高活性発現のメカニズムを探るために、反応過程における各元素のリーチング量をICP-MASSで測定し、リーチングは反応に関与していないことを確認した。また、Pdの価数を調べるために放射光を用いたより精密な実験を行った。また、ルテニウム触媒を用いる環化異性化反応を見出し置換インドリデンの新しい合成法を発見した。

Report

(3 results)
  • 2004 Annual Research Report
  • 2003 Annual Research Report
  • 2002 Annual Research Report
  • Research Products

    (17 results)

All 2004 2003 2002 Other

All Journal Article (7 results) Patent(Industrial Property Rights) (2 results) Publications (8 results)

  • [Journal Article] Novel Palladium Catalyst Supported on GaAs(001) Passivated by Ammonium-sulfide2004

    • Author(s)
      I.Takamiya, S.Tsukamoto, M.Shimoda, N.Miyashita, M.Arisawa, Y.Arakawa, A.Nishida
    • Journal Title

      Chemistry Letters 33(9)

      Pages: 1208-1209

    • NAID

      10013528105

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Cycloisomerization Promoted by the Combination of a Ruthenium Carbene Catalyst and Trimethylsilyl Vinyl Ether, and its Application in The Synthesis of Heterocyclic Compounds: 3-Methylene-2,3-dihydroindoles and 3-Methylene-2004

    • Author(s)
      Y.Terada, M.Arisawa, M.Nakagawa, A.Nishida
    • Journal Title

      Angewandte Chemie International Edition 43(31)

      Pages: 4063-4067

    • Related Report
      2004 Annual Research Report
  • [Journal Article] A novel synthesis of substituted quinolines using ring-closing metathesis (RCM): its application to the synthesis of key intermediates for anti-malarial agents2004

    • Author(s)
      C.Theeraladanon, M.Arisawa, M.Nakagawa, A.Nishida
    • Journal Title

      Tetrahedron 60(47)

      Pages: 3017-3035

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Preparative Synthesisof3,4,4a,5,8,8a-Hexahydro-2H-isoquinolin-1-one Ring System by the Diels-Alder Reaction of Optically Active Dienophile,5,6-Dihydro-1H-pyridin-2-one derivative with Siloxydiene2003

    • Author(s)
      Masako Nakagawa, Hideharu Uchida, Takeshi Watanabe, Yoshiyuki Kimura, Mariko Yamabe, Koji Ono, Riichiro Tsuji, Masakatsu Akiba, Yukiyoshi Terada, Dai Nagaki, Sachiko Ban, Naoki Miyashita, Takuya Kano, Chumpol Theeraladanon, Keisuke Hatakeyama, Mitsuhiro Arisawa, Atsushi Nishida
    • Journal Title

      Heterocycles 59(2)

      Pages: 721-733

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Novel Organopalladium Material Formed on a Sulfur-Terminated GaAs(001) Surface2002

    • Author(s)
      M.Arisawa, S.Tsukamoto, M.Shimoda, M.Pristovsek, A.Nishida
    • Journal Title

      Journal of Applied Physics 41(11A)

    • NAID

      110004080935

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Selective Isomerization of Terminal Olefin Catalyzed by a RutheniumComplex : A Novel Indole Synthesis via Ring-Closing Metathesis (RCM)2002

    • Author(s)
      M.Arisawa, Y.Terada, M.Nakatawa, A.Nishida
    • Journal Title

      Angewandte Chemie International Edition 41(24)

      Pages: 4732-4734

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Novel synthetic method for 2,3-Dihydro-3-halo-3-methylindole from N-Acetyl-2-isopropenylaniline by intramolecular haloamination2002

    • Author(s)
      M.Arizona, Y.Ando, M.Yamanaka, M.Nakagawa, A.Nishida
    • Journal Title

      Synlett 9

      Pages: 1514-1516

    • Related Report
      2004 Annual Research Report
  • [Patent(Industrial Property Rights)] 金属触媒、及びその製造方法2004

    • Inventor(s)
      西田 篤司, 塚本 史郎, 下田 正彦, 有澤 光弘
    • Industrial Property Rights Holder
      JST,物質・材料研究機構
    • Industrial Property Number
      2004-091736
    • Filing Date
      2004-03-26
    • Related Report
      2004 Annual Research Report
  • [Patent(Industrial Property Rights)] 基板結合型遷移金属触媒、及びその製造方法2002

    • Inventor(s)
      西田 篤司, 塚本 史郎, 下田 正彦, 有澤 光弘
    • Industrial Property Rights Holder
      JST,物質・材料研究機構
    • Industrial Property Number
      2002-299141
    • Filing Date
      2002
    • Related Report
      2004 Annual Research Report
  • [Publications] M.Arisawa, S.Tsukamoto, M.Shimoda, M.Pristovesk, A.Nishida: "Novel Organopalladium Material Formed on a Sulfur-Terminated GaAs(001) Surface"Jpn.J.Appl.Phys.. 41. L1197-L1199 (2002)

    • Related Report
      2003 Annual Research Report
  • [Publications] Mitsuhiro Arisawa, Yukiyoshi Terada, Masako Nakagawa, Atsushi Nishida: "Selective Isomerization of Terminal Olefin Catalyzed by a Ruthenium Complex : A Novel Indole Synthesis via Ring-Closing Metathesis (RCM)"Angewandte Chemie International Edition. 41(24). 4732-4734 (2002)

    • Related Report
      2003 Annual Research Report
  • [Publications] Mitsuhiro Arisawa, Yuko Ando, Masamichi Yamanaka, Masako Nakagawa, Atsushi Nishida: "Novel synthetic method for 2,3-Dihydro-3-halo-3-methylindole from N-Acetyl-2-isopropenylaniline by intramolecular haloamination"Synlett. 1514-1516 (2002)

    • Related Report
      2003 Annual Research Report
  • [Publications] Masako Nakagawa, Hideharu Uchida, Takeshi Watanabe, Yoshiyuki Kimura, Mariko Yamabe, Koji Ono, Riichiro Tsuji, Masakatsu Akiba, Yukiyoshi Terada, Dai Nagaki, Sachiko Ban, Naoki Miyashita, Takuya Kano, Chumpol Theeraladanon, Keisuke Hatakeyama, Mitsuhiro Arisawa, Atsushi Nishida: "Preparative Synthesis of 3,4,4a,5,8,8a-Hexahydro-2H-isoquinolin-1-one Ring System by the Diels-Alder Reaction of Optically Active Dienophile, 5,6-Dihydro-1H-pyridin-2-one derivative with Siloxydiene"Heterocycles. 59(2). 721-733 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Mitsuhiro Arisawa, Shiro Tsukamoto, Masahiko Shimoda, Markus Pristovsek, Atsushi Nishida: "Novel organopalladium catalyst material formed on a sulfur-terminated GaAs(001) surface"Japanese Journal of Applied Physics. 41. L1197-L1199 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Mitsuhiro Arisawa, Yukiyoshi Terada, Masako Nakagawa, Atsushi Nishida: "Selective Isomerization of Terminal Olefin Catalyzed by a Ruthenium Complex : A Novel Indole Synthesis via Ring-Closing Metathesis (RCM)"Angewandte Chemie International Edition. 41(24). 4732-4734 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Mitsuhiro Arisawa, Yuko Ando, Masamichi Yamanaka, Masako Nakagawa, Atsushi Nishida: "Novel synthetic method for 2,3-Dihydro-3-halo-3-methylindole from N-Acetyl-2-isopropenylaniline by intramolecular haloamination"Synlett. 1514-1516 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Masako Nakagawa, Hideharu Uchida, Takeshi Watanabe, Yoshiyuki Kimura, Mariko Yamabe, Koji Ono, Riichiro Tsuji, Masakatsu Akiba, Yukiyoshi Terada, Dai Nagaki, Sachiko Ban, Naoki Miyashita, Takuya Kano, Chumpol Theeraladanon, Keisuke Hatakeyama, Mitsuhiro Arisawa, Atsushi Nishida: "Preparative Synthesis of 3,4,4a,5,8,8a-Hexahydro-2H-isoquinolin-1-one Ring System by the Diels-Alder Reaction of Optically Active Dienophile, 5,6-Dihydro-1H-pyridin-2-one derivative with Siloxydiene"Heterocycles. 59(2). 721-733 (2003)

    • Related Report
      2002 Annual Research Report

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Published: 2002-04-01   Modified: 2016-04-21  

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