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Stereocontrol with planar-chiral pyridines by using structually unique properties of their ansa-bridges

Research Project

Project/Area Number 19550112
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Synthetic chemistry
Research InstitutionWaseda University

Principal Investigator

KANOMATA Nobuhiro  Waseda University, 理工学術院, 教授 (40221890)

Project Period (FY) 2007 – 2008
Project Status Completed (Fiscal Year 2008)
Budget Amount *help
¥4,680,000 (Direct Cost: ¥3,600,000、Indirect Cost: ¥1,080,000)
Fiscal Year 2008: ¥1,040,000 (Direct Cost: ¥800,000、Indirect Cost: ¥240,000)
Fiscal Year 2007: ¥3,640,000 (Direct Cost: ¥2,800,000、Indirect Cost: ¥840,000)
Keywords触媒設計・反応 / 不斉合成 / 面不斉 / ピリジノファン / 不斉シクロプロパン化 / ピリジニウムイリド / ビピリジン / テルピリジン / ターピリジン / アトロプ異性 / 選択的合成・反応 / アトロブ異性
Research Abstract

面不斉架橋ピリジニウムイリドを用いて電子不足系アルケンとの反応を検討し, 極めて高立体選択的に不斉シクロプロパン化が進行することを見いだした. 特にイリド架橋鎖の反対側に嵩高い置換基を導入することで, 全く新しい遠隔立体効果を機能させることに成功し, 不斉収率が飛躍的に向上することを突き止めた. 一方, C2対称性を有する新規な面不斉ビピリジン・テルピリジンの合成法を確立し, 銅触媒存在下, ジアゾ酢酸エチルとスチレンの反応による触媒的不斉シクロプロパン化反応を検討した. いずれも良好な立体選択性と触媒活性を示し, テルピリジン配位子においては顕著な遠隔立体効果が観測され, 飛躍的に立体選択性が向上した.

Report

(3 results)
  • 2008 Annual Research Report   Final Research Report ( PDF )
  • 2007 Annual Research Report
  • Research Products

    (17 results)

All 2009 2008 2007

All Journal Article (3 results) (of which Peer Reviewed: 3 results) Presentation (14 results)

  • [Journal Article] Synthesis of planar-chiral bridged bipyridines and terpyridines by metal-mediated coupling reactions of pyridinophanes2009

    • Author(s)
      Nobuhiro Kanomata, Jun Suzuki, Hironobu Kubota, Kiichiro Nishimura, and Terumichi Enomoto
    • Journal Title

      Tetrahedron Lett 50

      Pages: 2740-2743

    • Related Report
      2008 Final Research Report
    • Peer Reviewed
  • [Journal Article] Synchronized stereocontrol of planar chirality by crystallization-induced asymmetric transformation2009

    • Author(s)
      Nobuhiro Kanomata, Gou Mishima, and Jun Onozato
    • Journal Title

      Tetrahedron Lett 50

      Pages: 409-412

    • Related Report
      2008 Final Research Report
    • Peer Reviewed
  • [Journal Article] Synchronized stereocontrol of planar chirality by crystallization-induced asymmetric transformation2009

    • Author(s)
      鹿又宣弘, 鈴木潤, 久保田博信, 西村紀一郎, 榎本光伯
    • Journal Title

      Tetrahedron Letters 50(印刷中)

    • Related Report
      2008 Annual Research Report
    • Peer Reviewed
  • [Presentation] Efficient synthesis of C2-symmetric planar-chiral bipyridines and their asymmetric cyclopropanation reactions2008

    • Author(s)
      Kiichiro Nishimura and Nobuhiro Kanomata
    • Organizer
      236th ACS National Meeting
    • Place of Presentation
      Philadelphia in U.S.A.
    • Related Report
      2008 Final Research Report
  • [Presentation] Remote steric effect on enantioselective cyclopropanation reactions with planar-chiral pyridinophanes2008

    • Author(s)
      Nobuhiro Kanomata, Ryo Sakaguchi, Kazuki Kimura, Hironobu Kubota, and Kazuki Sekine
    • Organizer
      235th ACS National Meeting
    • Place of Presentation
      New Orleans in U.S.A.
    • Related Report
      2008 Final Research Report
  • [Presentation] C_2対称面不斉ビピリジノファンの合成法の開発とその不斉シクロプロパン化反応2008

    • Author(s)
      西村紀一郎・鹿又宣弘・鈴木潤
    • Organizer
      複素環化学討論会
    • Place of Presentation
      福山
    • Related Report
      2008 Final Research Report
  • [Presentation] 面不斉ピリジニウムイリドを用いた高エナンチオ選択的シクロプロパン化反応2008

    • Author(s)
      阪口良・鹿又宣弘
    • Organizer
      日本化学会第88春季年会
    • Place of Presentation
      東京
    • Related Report
      2008 Final Research Report 2007 Annual Research Report
  • [Presentation] C_2対称面不斉ビピリジンの効率的合成法の開発とその不斉シクロプロパン化反応2008

    • Author(s)
      西村紀一郎・鹿又宣弘
    • Organizer
      日本化学会第88春季年会
    • Place of Presentation
      東京
    • Related Report
      2008 Final Research Report
  • [Presentation] Remote steric effect on enantioselective cyclopropanation reactions with planar-chiral pyridinophanes2008

    • Author(s)
      鹿又宣弘, 阪口良, 木村一樹, 久保田博信, 関根一基
    • Organizer
      235th ACS National Meeting
    • Place of Presentation
      New Orleans
    • Related Report
      2008 Annual Research Report
  • [Presentation] Efficient synthesis of C2-symmetric planar-chiral bipyridines and their asymmetric cyolopropanation reactions2008

    • Author(s)
      西村紀一郎, 鹿又宣弘
    • Organizer
      236th ACS National Meeting
    • Place of Presentation
      Philadelphia
    • Related Report
      2008 Annual Research Report
  • [Presentation] C2対称面不斉ビピリジノファンの合成法の開発とその不斉シクロプロパン化反応2008

    • Author(s)
      西村紀一郎, 鹿又宣弘, 鈴木潤
    • Organizer
      複素環化学討論会
    • Place of Presentation
      福山
    • Related Report
      2008 Annual Research Report
  • [Presentation] C2対称面不斉ビピリジンの効率的合成法の開発とその不斉シクロプロパン化反応2008

    • Author(s)
      西村 紀一郎・鹿又 宣弘
    • Organizer
      日本化学会第88春季年会
    • Place of Presentation
      東京
    • Related Report
      2007 Annual Research Report
  • [Presentation] 面不斉ピリジノファン架橋鎖の動的挙動とその立体効果2008

    • Author(s)
      鹿又 宣弘・木村 一樹
    • Organizer
      日本化学会第88春季年会
    • Place of Presentation
      東京
    • Related Report
      2007 Annual Research Report
  • [Presentation] Enantioselective cyclopropanation reactions with planar-chiral pyridinium ylides2007

    • Author(s)
      Nobuhiro Kanomata and Ryo Sakaguchi
    • Organizer
      21st International Congress of Heterocyclic Chemistry
    • Place of Presentation
      Sydney in Australia
    • Related Report
      2008 Final Research Report
  • [Presentation] 面不斉ピリジノファンの遠隔立体効果と不斉シクロプロパン化反応への応用2007

    • Author(s)
      鹿又宣弘・久保田博信・阪口良・関根一基・山下聡美・鈴木潤
    • Organizer
      複素環化学討論会
    • Place of Presentation
      長野
    • Related Report
      2008 Final Research Report
  • [Presentation] Enantioselective cyclopropanation reactions with planar-chiral pyridinium ylides2007

    • Author(s)
      Nobuhiro Kanomata and Ryo Sakaguchi
    • Organizer
      21st International Congress of-Heterocyclic Chemistry
    • Place of Presentation
      Sydney,Australia
    • Related Report
      2007 Annual Research Report
  • [Presentation] 面不斉ピリジノファンの遠隔立体効果と不斉シク呈プロパン化反応への応用2007

    • Author(s)
      鹿又 宣弘・久保田 博信・阪口 良・関根 一基・山下 聡美・鈴木 潤
    • Organizer
      第37回複素環化学討論会
    • Place of Presentation
      長野
    • Related Report
      2007 Annual Research Report

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

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