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Development of novel fused planar-chiral catalysts and their asymmetric catalysis based on the concept of dynamism control

Research Project

Project/Area Number 15K13649
Research Category

Grant-in-Aid for Challenging Exploratory Research

Allocation TypeMulti-year Fund
Research Field Organic chemistry
Research InstitutionWaseda University

Principal Investigator

KANOMATA Nobuhiro  早稲田大学, 理工学術院, 教授 (40221890)

Project Period (FY) 2015-04-01 – 2017-03-31
Project Status Completed (Fiscal Year 2016)
Budget Amount *help
¥4,030,000 (Direct Cost: ¥3,100,000、Indirect Cost: ¥930,000)
Fiscal Year 2016: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Fiscal Year 2015: ¥2,600,000 (Direct Cost: ¥2,000,000、Indirect Cost: ¥600,000)
Keywordsピリジノファン / 面不斉 / 有機触媒 / 遠隔立体効果 / 不斉シクロプロパン化 / ラセミ化 / ピリジニウムイリド
Outline of Final Research Achievements

We have designed and synthesized novel planar-chiral parapyridinophane catalysts of the 2nd generation, whose ansa-bridges are tethered to a part of their pyridine rings to freeze their characteristic rope-skipping racemization even at higher temperatures. Pyridinophane catalysts fused with six membered ring effected highly enantioselective ylide-mediated cyclopropanation reactions to afford optically active trans-cyclopropanes exclusively with excellent enantiomeric excesses. For pyridinophane catalysts fused with five membered ring, their catalytic abilities were improved remarkably by introducing remote steric effect: incorporation of large substituents on such pyridine catalysts exerted a significant increase of enantioselectivity close to the level of the catalyst fused with six membered ring. Consequently, we have developed successfully novel fused pyridinophane catalysts with higher planar-chiral stability to achieve high level of asymmetric induction as organocatalysts.

Report

(3 results)
  • 2016 Annual Research Report   Final Research Report ( PDF )
  • 2015 Research-status Report
  • Research Products

    (6 results)

All 2017 2016 2015

All Journal Article (2 results) (of which Peer Reviewed: 2 results) Presentation (4 results) (of which Int'l Joint Research: 1 results)

  • [Journal Article] Remote steric effects of C2-symmetric planar-chiral terpyridine ligands on copper-catalyzed asymmetric cyclopropanation reactions2015

    • Author(s)
      Nanako Mugishima, Nobuhiro Kanomata, Norihiko Akutsu, Hironobu Kubota
    • Journal Title

      Tetrahedron Letters

      Volume: 56 Issue: 14 Pages: 1898-1903

    • DOI

      10.1016/j.tetlet.2015.02.103

    • Related Report
      2015 Research-status Report
    • Peer Reviewed
  • [Journal Article] Azaspirene analogs inhibit the growth of human uterine carcinosarcoma in vitro and in vivo2015

    • Author(s)
      Makoto Emoto, Kyoko Yano, Batsuren Choijamts, Shinnosuke Sakai, Shun Hirasawa, Shinnosuke Wakamori, Mamoru Aizawa, Kazuki Nabeshima, Katsuro Tachibana, Nobuhiro Kanomata
    • Journal Title

      Anticancer Research

      Volume: 35 Pages: 2739-2746

    • Related Report
      2015 Research-status Report
    • Peer Reviewed
  • [Presentation] 架橋鎖にsp2炭素を有する面不斉ピリジノファンの架橋鎖反転における加速効果2017

    • Author(s)
      宮下裕輔,菊池貴大,鹿又宣弘
    • Organizer
      日本化学会第97春季年会
    • Place of Presentation
      横浜
    • Year and Date
      2017-03-16
    • Related Report
      2016 Annual Research Report
  • [Presentation] パラピリジノファンの面不斉反転における立体効果と電子的効果2016

    • Author(s)
      宮下裕輔,木村一樹,上嶋和弘,鹿又宣弘
    • Organizer
      第46回複素環化学討論会
    • Place of Presentation
      金沢
    • Year and Date
      2016-09-26
    • Related Report
      2016 Annual Research Report
  • [Presentation] Steric and electronic effects for rope-skipping dynamism of planar chiral cyclophanes and pyridinophanes2016

    • Author(s)
      宮下裕輔,木村一樹,上嶋和弘,鹿又宣弘
    • Organizer
      28th International Symposium on Chiral Discrimination (ISCD28, Chilarity2016)
    • Place of Presentation
      Heidelberg, Germany
    • Year and Date
      2016-07-24
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research
  • [Presentation] 縮環型面不斉ピリジンの触媒機能と立体効果2015

    • Author(s)
      宮下裕輔, 鹿又宣弘
    • Organizer
      モレキュラー・キラリティー2015
    • Place of Presentation
      東京
    • Year and Date
      2015-06-12
    • Related Report
      2015 Research-status Report

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Published: 2015-04-16   Modified: 2018-03-22  

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