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高い不斉誘起能を持つ新規複素環ユニット開発

Research Project

Project/Area Number 14044112
Research Category

Grant-in-Aid for Scientific Research on Priority Areas

Allocation TypeSingle-year Grants
Review Section Science and Engineering
Research InstitutionOkazaki National Research Institutes

Principal Investigator

魚住 泰広  岡崎国立共同研究機構, 分子科学研究所, 教授 (90201954)

Project Period (FY) 2002 – 2003
Project Status Completed (Fiscal Year 2003)
Budget Amount *help
¥4,500,000 (Direct Cost: ¥4,500,000)
Fiscal Year 2003: ¥2,300,000 (Direct Cost: ¥2,300,000)
Fiscal Year 2002: ¥2,200,000 (Direct Cost: ¥2,200,000)
Keywords有機化学 / 不斉合成 / 複素環 / 有機金属化学 / 触媒
Research Abstract

我々は本研究の過程で新規な不斉ユニットとしてhexahydro-1H-pyrrolo[l,2-c]imidazolone骨格を開発し,幾つかの触媒的不斉工程で高い立体選択性を達成してきた.今年度は特にこの骨格を不斉配位部位とするピンサー錯体の設計・調製および触媒反応への利用について検討した.
従来ピンサー型錯体はピンサー錯体は,対応するピンサー型配位子に対する遷移金属種の反応により調製される.しかしながら我々が標的とした錯体は配位子に対するパラジウム種の導入は全く進行しなかった.標的ピンサー錯体は予め両オルト位にホルミル基を導入したアリールパラジウム錯体とプロリンアニリドの縮合によって調製された.
調製されたピンサーパラジウム錯体の触媒的利用はヘック反応および不斉マイケル付加反応において検討された.ヨードベンゼンとアクリルエステルのヘック反応はNMP中140℃にて円滑に進行した.そのTONは5億,反応時間内における平均的TOFは6500/秒であった.
またhexahydro-1H-pyrrolo[1,2-c]imidazolone骨格を配位部位とする光学活性ピンサー錯体を触媒とするエチルビニルケトンとシアノプロピオン酸エステルのマイケル付加反応では目的生成物が高い立体選択性を伴いつつ定量的に得られ,特にイソプロピルエステルを用いた反応では最高83%eeの立体選択性を示し,不斉触媒としての可能性を示した.

Report

(2 results)
  • 2003 Annual Research Report
  • 2002 Annual Research Report
  • Research Products

    (19 results)

All Other

All Publications (19 results)

  • [Publications] Uozumi, Yasuhiro, Tanaka, Hirotaka, Shibatomi, Kazutaka: "Asymmetric Allylic Amination in Water Catalyzed by an Amphiphilic Resin-Supported Chiral Palladium Complex"Org.Lett.. 6. 281-283 (2004)

    • Related Report
      2003 Annual Research Report
  • [Publications] Hocke, Heiko, Uozumi, Yasuhiro: "A Simple Synthetic Approach to Homochiral 6- and 6'-substituted 1,1'-Binaphthyl Derivatives"Tetrahedron. 59. 619-630 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] 魚住 泰広: "水中機能性固定化パラジウム錯体触媒反応"ファルマシア. 39. 647-649 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Uozumi, Yasuhiro, Nakao, Ryu: "Catalytic Oxidation of Alcohols in Water under Atmospheric Oxygen by Use of an Amphiphilic Resin-Dispersion of Nano Palladium Catalyst"Angew.Chem.. 115. 204-207 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Uozumi, Yasuhiro, Kobayashi, Yukinari: "The Sonogashira Reaction in Water via An Amphiphilic Resin-Supported Palladium-Phosphine Complex Under Copper-Free Conditions"Heterocycles. 59. 71-74 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Uozumi, Yasuhiro, Kimura, Tsutomu: "Heck Reaction in Water with Amphiphilic Resin-Supported Palladium-Phosphine Complexes"Synlett. 12. 2045-2048 (2002)

    • Related Report
      2003 Annual Research Report
  • [Publications] Shibatomi, Kazutaka, Uozumi, Yasuhiro: "New homochiral phosphine ligands having a hexahydro-1H-pyrrolo[1,2-c]imidazolonebackbone : preparation and use for palladium-catalyzed asymmetric alkylation of cycloalkenyl carbonates"Tetrahedron : Asymmetry. 13. 1769-1772 (2002)

    • Related Report
      2003 Annual Research Report
  • [Publications] Uozumi, Yasuhiro, Nakai, Yasushi: "An Amphiphilic Resin-Supported Palladium Catalyst for High-Throughput Cross-Coupling in Water"Org.Lett.. 4. 2997-3000 (2002)

    • Related Report
      2003 Annual Research Report
  • [Publications] Uozumi, Yasuhiro: "Palladium Catalysis in Water : Design, Preparation, and Use of Amphiphilic Resin-Supported Palladium-Phosphine Complexes"J.Synth.Org.Chem.,Jpn. 60. 1063-1068 (2002)

    • Related Report
      2003 Annual Research Report
  • [Publications] 魚住 泰広: "先端化学シリーズI 有機金属/キラル/触媒/高分子 日本化学会編 不斉工程開発へのコンビナトリアルアプローチ"丸善株式会社. 99-105 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] 魚住 泰広: "先端化学シリーズV 海洋天然物/錯体/コンビナトリアル/全合成 日本化学会編 錯体触媒反応における近年のブレークスルー"丸善株式会社. 93-98 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Uozumi, Yasuhiro: "The Society of Synthetic Organic Chemistry, Japan My Favorite Organic Synthesis"Palladium Catalysis in Water. 2 (2002)

    • Related Report
      2003 Annual Research Report
  • [Publications] Uozumi, Yasuhiro, Nakao, Ryu: "Catalytic Oxidation of Alcohols in Water under Atmospheric Oxygen by Use of an Amphiphilic Resin-Dispersion of NanoPalladium Catalyst"Angew. Chem.. 115. 204-207 (2003)

    • Related Report
      2002 Annual Research Report
  • [Publications] Uozumi, Yasuhiro, Kobayashi, Yukinari: "The Sonogashira Reaction in Water via An Amphiphilic Resin-Supported Palladium-Phosphine Complex Under Copper-Free Conditions"Heterocycles. 59. 71-74 (2003)

    • Related Report
      2002 Annual Research Report
  • [Publications] Uozumi, Yasuhiro, Kimura, Tsutomu: "Heck Reaction in Water with Amphiphilic Resin-Supported Palladium-Phosphine Complexes"Synlett. 2045-2048 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Shibatomi, Kazutaka, Uozumi, Yasuhiro: "New homochiral phosphine ligands having a hexahydro-1H-pyrrolo[1,2-c]imidazolone backbone : preparation and use for palladium-catalyzed asymmetric alkylation of cycloalkenyl carbonates"Tetrahedron : Asymmetry. 13. 1769-1772 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Uozumi, Yasuhiro, Nakai, Yasushi: "An Amphiphilic Resin-Supported Palladium Catalyst for High-Throughput Cross-Coupling in Water"Org. Lett.. 4. 2997-3000 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Uozumi, Yasuhiro: "Palladium Catalysis in Water : Design, Preparation, and Use of Amphiphilic Resin-Supported Palladium-Phosphine Complexes"J. Synth. Org. Chem., Jpn. 60. 1063-1068 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Uozumi, Yasuhiro: "The Society of Synthetic Organic Chemistry, Japan My Favorite Organic Synthesis"Palladium Catalysis in Water. 2 (2002)

    • Related Report
      2002 Annual Research Report

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Published: 2002-04-01   Modified: 2018-03-28  

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