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超分子相互作用を有する遷移金属分子触媒の創製

Research Project

Project/Area Number 19655033
Research Category

Grant-in-Aid for Exploratory Research

Allocation TypeSingle-year Grants
Research Field Synthetic chemistry
Research InstitutionKyoto University

Principal Investigator

辻 康之  Kyoto University, 工学研究科, 教授 (30144330)

Project Period (FY) 2007 – 2008
Project Status Completed (Fiscal Year 2008)
Budget Amount *help
¥3,400,000 (Direct Cost: ¥3,400,000)
Fiscal Year 2008: ¥1,900,000 (Direct Cost: ¥1,900,000)
Fiscal Year 2007: ¥1,500,000 (Direct Cost: ¥1,500,000)
Keywordsデンドリマー / メタセシス / ルテニウム錯体 / 配位子 / 触媒活性 / 結晶構造 / 半球型ホスフィン / カリックスアレーン / 超分子相互作用 / 分子触媒
Research Abstract

本研究においては,デンドリマー触媒のさらなる応用範囲の開拓を目的とし、柔軟なポリエーテルデンドリマーを組み込んだ新規NHC配位子を設計・合成した。配位子の有効性を評価するため、ルテニウム錯体を合成し、オレフィンメタセシス反応における触媒活性を検討した。配位子の外側にデンドリマーを組み込むことより、中心金属近傍には空間を保持し、金属から離れた位置には嵩高い立体を有する反応場が構築できると考えた。導入するデンドリマーは、構造が柔軟で多様な立体構造をとることが可能であり、かつ、様々な反応に対して比較的安定なポリベンジルエーテル型のデンドリマーを選択した。配位子前駆体となるイミダゾリニウム塩は、種々の合成経路を検討した結果、第3世代(G3)までの合成に成功した。出発原料から三段階で合成し、いずれの段階も中程度以上の収率で生成物を得た。こうして得られた配位子前駆体を用いて、メタセシス触媒となるルテニウム錯体を合成し、第2世代(G2)までの合成に成功した。得られた錯体のうち、第0世代の錯体についてはX線結晶構造解析により、その結晶構造を決定した。Grubbs-Hoveyda触媒との比較検討は、オレフィンメタセシス反応の触媒活性の検証に一般的に用いられるマロン酸ジエチル誘導体の閉環メタセシス反応で行った。5員環の環状オレフィンを与えるジアリルマロン酸ジエチルを用いて反応行ったところ、いずれの触媒でも反応がほぼ定量的に進行した。デンドリマー部位は反応を阻害することなく、メタセシス触媒として有効に機能することがわかった。

Report

(2 results)
  • 2008 Annual Research Report
  • 2007 Annual Research Report
  • Research Products

    (35 results)

All 2008 2007

All Journal Article (13 results) (of which Peer Reviewed: 12 results) Presentation (22 results)

  • [Journal Article] Kinetic Resolution of Phosphoryl and Sulfonyl Esters of 1, 1'-Bi-2 naphthol via Pd-catalyzed Alcoholysis of their Vinyl Ethers.2008

    • Author(s)
      T. Sakuma, E. Yamamoto, H. Aoyama, Y. Obora, Y. Tsuji, M.
    • Journal Title

      Tetrahedron : Asymmetry 19

      Pages: 1593-1599

    • Related Report
      2008 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Iridium-catalyzed Decarbonylation of Aldehydes under Mild Conditions2008

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

      Chem. Commun.

      Pages: 6215-6217

    • Related Report
      2008 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Triarylphosphanes with Dendritically Arranged Tetraethylene Glycol Moieties at the Periphery2008

    • Author(s)
      T. Fujihara, S. Yoshida, H. Ohta, Y. Tsuji
    • Journal Title

      Angew. Chem. Int. Ed 47

      Pages: 8310-8314

    • Related Report
      2008 Annual Research Report
    • Peer Reviewed
  • [Journal Article] N-Heterocyclic Carbene Ligands Bearing Hydrophilic and/or Hydrophobic Chains: Rh(I)and Pd(II)Complexes2008

    • Author(s)
      H. Ohta, T. Fujihara, Y. Tsuji
    • Journal Title

      Dalton Trans

      Pages: 379-385

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Recent Development of Homogeneous Transition Metal Catalysts with Nanosize Ligands2007

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

      Chem. Lett

      Pages: 1296-1301

    • NAID

      10019791838

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Homogeneous Nanosize Palladium Catalysts2007

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

      Inorg. Chem., 46

      Pages: 1895-1902

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] New Design in Homogeneous Palladium Catalysis: Study of Transformation of Group 14 Element Compounds and Development of Nanosize Palladium Catalysts2007

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

      Bull. Korean Chem. Soc., 29

      Pages: 1902-1909

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Palladium-catalyzed Oxidation of Cyclohexanones to Conjugated Enones Using Molecular Oxygen2007

    • Author(s)
      M. Tokunaga, S. Harada, T. Iwasawa, Y. Obora, Y. Tsuji
    • Journal Title

      Tetrahedron Lett. 48

      Pages: 6860-6862

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Rhodium(III)Complexes with a Bidentate N-Heterocyclic Carbene Ligand Bearing Flexible Dendritic Frameworks2007

    • Author(s)
      T. Fujihara, Y. Obora, M. Tokunaga, Y. Tsuji
    • Journal Title

      Dalton Trans.,

      Pages: 1567-1569

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] A Bowl-Shaped Phosphine as a Ligand in Palladium-Catalyzed Suzuki-Miyaura Coupling of Aryl Chlorides: Effect of a Depth of the Bowl2007

    • Author(s)
      H. Ohta, M. Tokunaga, Y. Obora, T. Iwai, T. Iwasawa, T. Fujihara, Y. Tsuji
    • Journal Title

      Org. Lett., 9

      Pages: 89-92

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] かごのなかに閉じ込められた有機金属錯体2007

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

      化学 62

      Pages: 66-67

    • Related Report
      2007 Annual Research Report
  • [Journal Article] Rhodium(I)Complexes with N-Heterocyclic Carbenes Bearing a 2,3,4,5-Tetraphenylphenyl and Its Higher Dendritic Frameworks2007

    • Author(s)
      H. Sato, T. Fujihara, Y. Obora, M. Tokunaga, J. Kiyosu, Y. Tsuji
    • Journal Title

      Chem. Commun.

      Pages: 269-271

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Metal Complexes-catalyzed Hydrolysis and Alcoholysis of Organic Substrates and its Application to Kinetic Resolution2007

    • Author(s)
      M. Tokunaga, H. Aoyama, J. Kiyosu, Y. Shirogane, T. Iwasawa, Y. Obora, Y. Tsuji
    • Journal Title

      J. Organomet. Chem 692

      Pages: 4665-4669

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Presentation] 剛直なテトラフェニルフェニル基を有するルテニウム-メタセシス触媒の合成とその触媒活性2008

    • Author(s)
      ○富家嘉一, 大竹敏之, 藤原哲晶, 寺尾潤, 辻康之
    • Organizer
      第58回錯体化学討論会
    • Place of Presentation
      金沢(金沢大学)
    • Year and Date
      2008-09-20
    • Related Report
      2008 Annual Research Report
  • [Presentation] 柔軟なポリエーテルに覆われた含窒素ヘテロ環カルベン錯体の合成と触媒活性2008

    • Author(s)
      太田英俊、 藤原哲晶、 辻 康之
    • Organizer
      日本化学会第88春季年会
    • Place of Presentation
      東京
    • Year and Date
      2008-03-28
    • Related Report
      2007 Annual Research Report
  • [Presentation] 長鎖疎水基及び長鎖親水基を有する新規デンドリマーモノホスフィン配位子の合成と触媒反応への応用2008

    • Author(s)
      吉田昌平、太田英俊、藤原哲晶、辻 康之
    • Organizer
      日本化学会第88春季年会
    • Place of Presentation
      東京
    • Year and Date
      2008-03-28
    • Related Report
      2007 Annual Research Report
  • [Presentation] トリアゾール骨格を有する新規デンドリマーカルベン配位子の合成と機能2008

    • Author(s)
      小田 晋、藤原哲晶、辻 康之
    • Organizer
      日本化学会第88春季年会
    • Place of Presentation
      東京
    • Year and Date
      2008-03-28
    • Related Report
      2007 Annual Research Report
  • [Presentation] 剛直なテトラフェニルフェニル基を有するリン配位子を用いたルテニウム錯体の合成および触媒反応2008

    • Author(s)
      片渕優子、原田早紀、藤原哲晶、辻 康之
    • Organizer
      日本化学会第88春季年会
    • Place of Presentation
      東京
    • Year and Date
      2008-03-28
    • Related Report
      2007 Annual Research Report
  • [Presentation] 疎水性・親水性部位を有する含窒素ヘテロ環カルベン配位子の合成と触媒反応への応用2008

    • Author(s)
      太田英俊、藤原哲晶、辻 康之
    • Organizer
      日本化学会第88春季年会
    • Place of Presentation
      東京
    • Year and Date
      2008-03-28
    • Related Report
      2007 Annual Research Report
  • [Presentation] 塩化アリールの鈴木-宮浦カップリングにおける半球型ホスフィン配位子の効果2007

    • Author(s)
      太田英俊、辻 康之
    • Organizer
      2007年度 ナノテク合同公開シンポジウム
    • Place of Presentation
      横浜
    • Year and Date
      2007-11-29
    • Related Report
      2007 Annual Research Report
  • [Presentation] デンドリマーを基盤とするナノサイズ分子触媒の合成と触媒性能評価2007

    • Author(s)
      藤原哲晶、辻 康之
    • Organizer
      2007年度 ナノテク合同公開シンポジウム
    • Place of Presentation
      横浜
    • Year and Date
      2007-11-29
    • Related Report
      2007 Annual Research Report
  • [Presentation] Rh(I)and Rh(III)Complexes with N-Heterocyclic Carbene Ligands Bearing Frechet-type Flexible Dendritic Frameworks2007

    • Author(s)
      T. Fujihara, Y. Tsuji
    • Organizer
      2007 Workshop on Organometallic Chemistry
    • Place of Presentation
      和光市
    • Year and Date
      2007-11-08
    • Related Report
      2007 Annual Research Report
  • [Presentation] パラジウム触媒反応における半球型ホスフィン配位子の効果:溝呂木-Heck反応およびシリル化反応2007

    • Author(s)
      小畑貴慎、太田英俊、藤原哲晶、辻 康之
    • Organizer
      第54回有機金属化学討論会
    • Place of Presentation
      広島
    • Year and Date
      2007-10-28
    • Related Report
      2007 Annual Research Report
  • [Presentation] 親水基ならびに疎水基を導入した含窒素ヘテロ環カルベン配位子:設計・合成と触媒反応2007

    • Author(s)
      太田英俊、藤原哲晶、辻 康之
    • Organizer
      第54回有機金属化学討論会
    • Place of Presentation
      広島
    • Year and Date
      2007-10-27
    • Related Report
      2007 Annual Research Report
  • [Presentation] 長鎖疎水基及び長鎖親水基を有する新規デンドリマーモノホスフィン配位子の合成2007

    • Author(s)
      吉田昌平、太田英俊、藤原哲晶、辻 康之
    • Organizer
      第57回錯体化学討論会
    • Place of Presentation
      名古屋
    • Year and Date
      2007-09-26
    • Related Report
      2007 Annual Research Report
  • [Presentation] カリックス[6]アレーン部位を有する新規二座ホスフィン配位子の合成2007

    • Author(s)
      佐々木良一、藤原哲晶、辻 康之
    • Organizer
      第57回錯体化学討論会
    • Place of Presentation
      名古屋
    • Year and Date
      2007-09-25
    • Related Report
      2007 Annual Research Report
  • [Presentation] 柔軟なデンドリマー配位子を有するルテニウム-メタセシス触媒の合成と触媒性能2007

    • Author(s)
      西田 尊、藤原哲晶、辻 康之
    • Organizer
      第57回錯体化学討論会
    • Place of Presentation
      名古屋
    • Year and Date
      2007-09-25
    • Related Report
      2007 Annual Research Report
  • [Presentation] Palladium-Catalyzed Transformations of Aryl Halides Using Bowl-Shaped Phosphine as a Ligand2007

    • Author(s)
      H. Ohta, T. Kobatake, T. Fujihara, M. Tokunaga, Y. Obora, Y. Tsuji
    • Organizer
      4th International Symposium on Integrated Synthesis
    • Place of Presentation
      Hikone, Japan
    • Year and Date
      2007-09-23
    • Related Report
      2007 Annual Research Report
  • [Presentation] Dendritic Catalysts: Rhodium Complexes with N-Heterocyclic Carbene Ligands Having Flexible and Rigid Frameworks and Their Use in Hydrosilylation2007

    • Author(s)
      T. Fujihara, H. Sato, Y. Obora, M. Tokunaga, Y. Tsuji
    • Organizer
      4th International Symposium on Integrated Synthesis
    • Place of Presentation
      Hikone, Japan
    • Year and Date
      2007-09-23
    • Related Report
      2007 Annual Research Report
  • [Presentation] Rhodium(I)Complexes with N-Heterocyclic Carbene Ligands Bearing Flexible and Rigid Dendritic Frameworks2007

    • Author(s)
      T. Fujihara, H. Sato, Y. Obora, M. Tokunaga, Y. Tsuji
    • Organizer
      5th International Dendrimer Symposium
    • Place of Presentation
      Toulouse, France
    • Year and Date
      2007-08-29
    • Related Report
      2007 Annual Research Report
  • [Presentation] Effect of Bowl-Shaped Phosphine Ligands on the Palladium-Catalyzed Transformation of Aryl Halides2007

    • Author(s)
      H. Ohta, T. Kobatake, T. Fujihara, M. Tokunaga, Y. Obora, Y. Tsuji
    • Organizer
      The 14th IUPAC International Symposium on Organometallic Chemistry Directed Towards Organic Synthesis
    • Place of Presentation
      Nara, Japan
    • Year and Date
      2007-08-03
    • Related Report
      2007 Annual Research Report
  • [Presentation] Synthesis of Rhodium(I)Complexes with N-Heterocyclic Carbene Ligands Bearing Rigid Dendrimers and Their Use in Hydrosilylation2007

    • Author(s)
      T. Fujihara, H. Sato, Y. Obora, M. Tokunaga, Y. Tsuji
    • Organizer
      The 14th IUPAC International Symposium on Organometallic Chemistry Directed Towards Organic Synthesis
    • Place of Presentation
      Nara, Japan
    • Year and Date
      2007-08-03
    • Related Report
      2007 Annual Research Report
  • [Presentation] Cross-coupling Reaction using Low-valent Titanium and Niobium-alkyne Reagents2007

    • Author(s)
      Y. Obora, M. Kimura, H. Moriya, T. Ohtake, K. Takeshita, Y. Tada, M. Tokunaga, Y. Tsuji, Y. Ishii
    • Organizer
      The 14th IUPAC International Symposium on Organometallic Chemistry Directed Towards Organic Synthesis
    • Place of Presentation
      Nara, Japan
    • Year and Date
      2007-08-03
    • Related Report
      2007 Annual Research Report
  • [Presentation] Kinetic Resolution of Axially Chiral and P-Chirogenic Compounds via Palladium-Catalyzed Alcoholysis of Vinyl Ethers2007

    • Author(s)
      E. Yamamoto, T. Sakuma, H. Aoyama, Y. Obora, Y. Tsuji, M. Tokunaga
    • Organizer
      he 14th IUPAC International Symposium on Organometallic Chemistry Directed Towards Organic Synthesis
    • Place of Presentation
      Nara, Japan
    • Year and Date
      2007-08-03
    • Related Report
      2007 Annual Research Report
  • [Presentation] ナノサイズデンドリマー配位子を有する触媒システムとその機能2007

    • Author(s)
      辻 康之
    • Organizer
      公開シンポジウム「環境保全のためのナノ構造制御触媒及び新材料の創製」
    • Place of Presentation
      東京
    • Year and Date
      2007-04-19
    • Related Report
      2007 Annual Research Report

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Published: 2007-04-01   Modified: 2016-04-21  

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