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Synthesis of Heteroatom-Bridged Multinuclear Complexes and Application to Catalytic Transformations

Research Project

Project/Area Number 21750088
Research Category

Grant-in-Aid for Young Scientists (B)

Allocation TypeSingle-year Grants
Research Field Synthetic chemistry
Research InstitutionThe University of Tokyo

Principal Investigator

MIYAKE Yoshihiro  The University of Tokyo, 大学院・工学系研究科, 助教 (00347270)

Project Period (FY) 2009 – 2010
Project Status Completed (Fiscal Year 2010)
Budget Amount *help
¥4,550,000 (Direct Cost: ¥3,500,000、Indirect Cost: ¥1,050,000)
Fiscal Year 2010: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
Fiscal Year 2009: ¥2,860,000 (Direct Cost: ¥2,200,000、Indirect Cost: ¥660,000)
Keywords有機金属化学 / 有機合成化学
Research Abstract

Considerable attention has recently been paid to multimetallic complexes bridged by heteroatom ligands because of their potential applicability to various organic transformations. Recently, we disclosed a unique catalytic activity of thiolato- and selenolato-bridged diruthenium complexes [Cp^*RuCl(μ-YR)]_2 toward propargylic substitution reactions of propargylic alcohols with a variety of nucleophiles. In sharp contrast, tellurolato-bridged diruthenium complexes did not work as effective catalysts for these reactions, suggesting that the nature of bridging ligands plays an important role on the catalysis of these diruthenium complexes. These results prompted us to design and prepare other heteroatom-bridged diruthenium complexes. More recently, we succeeded in the preparation of the monophosphido-bridged diruthenium complex [Cp^*RuCl(μ-PMe_2)(μ-Cl)RuClCp^*] (1) and found a different catalytic activity of 1 from that of [Cp^*RuCl(μ-YR)]_2. In addition, 1 is expected to work as a useful precursor for diruthenium complexes bridged by different heteroatoms because 1 have a bridging chloride ligand which may easily be substituted with a variety of heteroatom ligands. In fact, we also succeeded in the preparation of a variety of hybrid phosphido- and thiolato-bridged complexes [Cp^*RuCl(μ-PMe_2)(μ-SR)RuClCp^*].

Report

(3 results)
  • 2010 Annual Research Report   Final Research Report ( PDF )
  • 2009 Annual Research Report
  • Research Products

    (15 results)

All 2010 2009 Other

All Journal Article (11 results) (of which Peer Reviewed: 5 results) Presentation (3 results) Remarks (1 results)

  • [Journal Article] Ruthenium-Catalyzed Enantioselective [3+3] Cycloaddition of Propargylic Alcohols with 2-Naphthols2010

    • Author(s)
      Keiichiro Kanao, Yoshihiro Miyake, Yoshiaki Nishibayashi
    • Journal Title

      Organometallics 29

      Pages: 2126-2131

    • Related Report
      2010 Final Research Report
  • [Journal Article] Cooperative Catalytic Reactions Using Organocatalysts and Transition Metal Catalysts : Enantioselective Propargylic Alkylation of Propargylic Alcohols withAldehydes2010

    • Author(s)
      Masahiro Ikeda, Yoshihiro Miyake, Yoshiaki Nishibayashi
    • Journal Title

      Angew.Chem.Int.Ed. 49

      Pages: 7289-7293

    • Related Report
      2010 Final Research Report
  • [Journal Article] Preparation of Thiolate-Bridged Dinuclear Ruthenium Complexes Bearing a Phosphine Ligand and Application to Propargylic Reduction of Propargylic Alcohols with 2-Propanol2010

    • Author(s)
      Masahiro Yuki, Yoshihiro Miyake, Yoshiaki Nishibayashi
    • Journal Title

      Organometallic 29

      Pages: 5994-6001

    • Related Report
      2010 Final Research Report
  • [Journal Article] Ruthenium-Catalyzed Enantioselective [3+3] Cycloaddition of Propargylic Alcohols with 2-Naphthols2010

    • Author(s)
      Keiichiro Kanao, Yoshihiro Miyake, Yoshiaki Nishibayashi
    • Journal Title

      Organometallics

      Volume: 29 Pages: 2126-2131

    • Related Report
      2010 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Cooperative Catalytic Reactions Using Organocatalysts and Transition Metal Catalysts : Enantioselective Propargylic Alkylation of Propargylic Alcohols withAld2010

    • Author(s)
      Masahiro Ikeda, Yoshihiro Miyake, Yoshiaki Nishibayashi
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 49 Pages: 7289-7293

    • Related Report
      2010 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Preparation of Thiolate-Bridged Dinuclear Ruthenium Complexes Bearing a Phosphine Ligand and Application to Propargylic Reduction of Propargylic Alcohols with 2-Propanol2010

    • Author(s)
      Masahiro Yuki, Yoshihiro Miyake, Yoshiaki Nishibayashi
    • Journal Title

      Organometallics

      Volume: 29 Pages: 5994-6001

    • Related Report
      2010 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Ruthenium-Catalyzed Enantioselective Intramolecular Propargylation of Thiophenes with Propargylic Alcohols2009

    • Author(s)
      Keiichiro Kanao, Yoshihiro Miyake, Yoshiaki Nishibayashi
    • Journal Title

      Organometallics 28

      Pages: 2920-2926

    • Related Report
      2010 Final Research Report 2009 Annual Research Report
  • [Journal Article] Design and Synthesis of Diphosphine Ligands Bearing an Osmium (II) Bis (terpyridyl) Moiety as a Light-Harvesting Unit : Application to Photocatalytic Production of Dihydrogen2009

    • Author(s)
      Yoshihiro Miyake, Kazunari Nakajima, Kouitsu Sasaki, Ryuichi Saito, Haruyuki Nakanishi, Yoshiaki Nishibayashi
    • Journal Title

      Organometallics 28

      Pages: 5240-5243

    • Related Report
      2010 Final Research Report
  • [Journal Article] Enantioselective Ring-Opening Reactions of Racemic Ethynyl Epoxides via Copper-Allenylidene Intermediates : Efficient Approach to Chiral β-Amino Alcohols2009

    • Author(s)
      Gaku Hattori, Akiko Yoshida, Yoshihiro Miyake, Yoshiaki Nishibayashi
    • Journal Title

      J.Org.Chem. 74

      Pages: 7603-7607

    • Related Report
      2010 Final Research Report
  • [Journal Article] Design and Synthesis of Diphosphine Ligands Bearing an Osmium(II)Bis(terpyridyl)Moiety as a Light-Harvesting Unit : Application to Photocatalytic Production of Dihydrogen2009

    • Author(s)
      Yoshihiro Miyake, Kazunari Nakajima, Kouitsu Sasaki, Ryuichi Saito, Haruyuki Nakanishi, Yoshiaki Nishibayashi
    • Journal Title

      Organometallics 28

      Pages: 5240-5243

    • Related Report
      2009 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Enantioselective Ring-Opening Reactions of Racemic Ethynyl Epoxides via Copper-Allenylidene Intermediates : Efficient Approach to Chiral β-Amino Alcohols2009

    • Author(s)
      Gaku Hattori, Akiko Yoshida, Yoshihiro Miyake, Yoshiaki Nishibayashi
    • Journal Title

      Journal of Organic Chemistry 74

      Pages: 7603-7607

    • Related Report
      2009 Annual Research Report
    • Peer Reviewed
  • [Presentation] Synthesis and Reactivity of Hybrid Phosphido-and Hydrosulfido-bridged Diruthenium Complex2010

    • Author(s)
      森山太一・遠藤聡・田辺資明・三宅由寛・西林仁昭
    • Organizer
      The 24th International Conference on Organometallic Chemistry
    • Year and Date
      2010-07-19
    • Related Report
      2010 Final Research Report
  • [Presentation] Synthesis and Reactivity of Hybrid Phosphido- and Hydrosulfido-bridged Diruthenium Complex2010

    • Author(s)
      森山太一・遠藤聡・田辺資明・三宅由寛・西林仁昭
    • Organizer
      The 24th International Conference on Organometallic Chemistry
    • Place of Presentation
      台湾,中国
    • Year and Date
      2010-07-19
    • Related Report
      2010 Annual Research Report
  • [Presentation] ルテニウム-アレニリデン錯体の新しい発生法の開発:エチニルシクロプロパンとアルデヒド及びアルジミンとの触媒的[3+3]環化付加反応2009

    • Author(s)
      森山太一・遠藤聡・三宅由寛・西林仁昭
    • Organizer
      第59回錯体化学討論会
    • Related Report
      2010 Final Research Report 2009 Annual Research Report
  • [Remarks] ホームページ等

    • Related Report
      2010 Final Research Report

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Published: 2009-04-01   Modified: 2016-04-21  

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