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Development of wide scope asymmetric dipolar cycloaddition reactions and its synthetic applications

Research Project

Project/Area Number 20200052
Research Category

Grant-in-Aid for Scientific Research on Innovative Areas (Research a proposed research project)

Allocation TypeSingle-year Grants
Research Field Synthetic chemistry
Drug development chemistry
Research InstitutionShinshu University

Principal Investigator

SUGA Hiroyuki  Shinshu University, 工学部, 教授 (60211299)

Project Period (FY) 2008 – 2010
Project Status Completed (Fiscal Year 2010)
Budget Amount *help
¥30,810,000 (Direct Cost: ¥23,700,000、Indirect Cost: ¥7,110,000)
Fiscal Year 2010: ¥9,360,000 (Direct Cost: ¥7,200,000、Indirect Cost: ¥2,160,000)
Fiscal Year 2009: ¥10,270,000 (Direct Cost: ¥7,900,000、Indirect Cost: ¥2,370,000)
Fiscal Year 2008: ¥11,180,000 (Direct Cost: ¥8,600,000、Indirect Cost: ¥2,580,000)
Keywords不斉合成・反応 / 生物活性物質 / 1,3-双極子 / 付加環化 / キラルルイス酸 / 分子触媒 / 不斉誘起 / エナンチオ選択性 / ジアステレオ選択性 / 親双極子剤 / 1, 3-双極子
Research Abstract

A generality for diazo substrates was widely expanded in the Lewis acid catalyzed asymmetric cycloaddition reactions of cyclic carbonyl ylides generated from diazo carbonyl compounds. For example, highly enantioselective cycloadditions of a cyclic carbonyl ylide generated from a diazo compound containing a pyrrolidine ring could be successfully applied to an asymmetric total synthesis of (+)-Tashiromine. High levels of asymmetric induction were also found to obtain in the similar asymmetric cycloaddition reactions of cyclic azomethine ylides generated from diazo imine derivatives. The chiral Ni(II) complexes originally developed in our laboratory was also found to be effective catalysts for a wide scope of use in asymmetric cycloaddition reactions of nitrile oxides, diazo esters, and cyclic ylides.

Report

(4 results)
  • 2010 Annual Research Report   Final Research Report ( PDF )
  • 2009 Annual Research Report
  • 2008 Annual Research Report
  • Research Products

    (28 results)

All 2011 2010 2009 2008 Other

All Journal Article (6 results) (of which Peer Reviewed: 6 results) Presentation (20 results) Book (1 results) Remarks (1 results)

  • [Journal Article] Asymmetric1,3-Dipolar Cycloaddition Reactions of Azomethine Imines with Acrolein Catalyzed by L-Proline and Its Derivatives2010

    • Author(s)
      Hiroyuki SUGA, Tadashi ARIKAWA, Kennosuke ITOH, Yukihisa OKUMURA, Akikazu KAKEHI, Motoo SHIRO
    • Journal Title

      Heterocycles 81,(7)

      Pages: 1669-1688

    • Related Report
      2010 Final Research Report
    • Peer Reviewed
  • [Journal Article] Inverse Electron Demand Asymmetric Cycloadditions of Cyclic Carbonyl Ylides Catalyzed by Chiral Lewis Acids-Scope and Limitations of Diazo and Olefinic Substrates2010

    • Author(s)
      Hiroyuki SUGA, Satoshi HIGUCHI, Motoo OHTSUKA, Daisuke ISHIMOTO, Tadashi ARIKAWA, Yuta HASHIMOTO, Shunta MISAWA, Teruko TSUCHIDA, Akikazu KAKEHI, Toshihide BABA
    • Journal Title

      Tetrahedron 66,(16)

      Pages: 3070-3089

    • Related Report
      2010 Final Research Report
    • Peer Reviewed
  • [Journal Article] ASYMMETRIC 1,3-DIPOLAR CYCLOADDITION REACTIONS OF AZOMETHINE IMINES WITH ACROLEIN CATALYZED BY L-PROLINE AND ITS DERIVATIVES.2010

    • Author(s)
      Hiroyuki Suga
    • Journal Title

      Heterocycles

      Volume: 81 Pages: 1669-1688

    • Related Report
      2010 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Inverse electron demand asymmetric cycloadditions of cyclic carbonylylides catalyzed by chiral Lewis acids-Scope and limitations of diazo and olefinic substrates2010

    • Author(s)
      Hiroyuki Suga
    • Journal Title

      Tetrahedron 66

      Pages: 3070-3089

    • Related Report
      2009 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Asymmetric 1,3-Dipolar Cycloaddition Reactions of Nitrile Oxides Catalyzed by Chiral Binaphthyldiimine-Ni(II) Complexes2009

    • Author(s)
      Hiroyuki SUGA, Yuki ADACHI, Kouhei FUJIMOTO, Yasuhisa FURIHATA, Teruko TSUCHIDA, Akikazu KAKEHI, Toshihide BABA
    • Journal Title

      J.Org.Chem. 74,(3)

      Pages: 1099-1113

    • Related Report
      2010 Final Research Report
    • Peer Reviewed
  • [Journal Article] Asymmetric 1, 3-Dipolar Cycloaddition Reactions of Nitrile Oxides Catalyzed by Chiral Binaphthyldiimine-Ni(II) Complexes2009

    • Author(s)
      Hiroyuki Suga
    • Journal Title

      J. Org. Chem 74

      Pages: 1099-1113

    • Related Report
      2008 Annual Research Report
    • Peer Reviewed
  • [Presentation] ビナフチジルイミン-Ni(II)触媒を用いるα-置換-α-ジアゾエステルとアルケン酸誘導体との不斉1,3-双極性付加環化反応2011

    • Author(s)
      菅博幸
    • Organizer
      日本化学会第91春季年会
    • Place of Presentation
      神奈川
    • Year and Date
      2011-03-29
    • Related Report
      2010 Annual Research Report 2010 Final Research Report
  • [Presentation] 非環状カルボニルイリドとキラル補助基を有する3-(2-アルケノイル)-2-オキサゾリジノン類とのジアステレオ選択的ルイス酸触媒1,3-双極性付加環化反応2011

    • Author(s)
      菅博幸
    • Organizer
      日本化学会第91春季年会
    • Place of Presentation
      神奈川
    • Year and Date
      2011-03-29
    • Related Report
      2010 Annual Research Report 2010 Final Research Report
  • [Presentation] ジアゾカルボニル化合物より発生させた環状カルボニルイリドとインドール誘導体とのキラルルイス酸触媒不斉付加環化反応2011

    • Author(s)
      菅博幸
    • Organizer
      日本化学会第91春季年会
    • Place of Presentation
      神奈川
    • Year and Date
      2011-03-29
    • Related Report
      2010 Annual Research Report 2010 Final Research Report
  • [Presentation] Asymmetric 1,3-dipolar cycloaddition reactions catalyzed by Pybox-, BINIM-, and BINAN-metal complexes2010

    • Author(s)
      菅博幸
    • Organizer
      Pacifichem 2010 Congress
    • Place of Presentation
      ホノルル(ハワイ)
    • Year and Date
      2010-12-18
    • Related Report
      2010 Annual Research Report 2010 Final Research Report
  • [Presentation] ジアゾイミド誘導体より発生させたカルボニルイリドの触媒的不斉付加環化と合成化学的応用2010

    • Author(s)
      菅博幸
    • Organizer
      第41回中部化学関係学協会支部連合秋季大会
    • Place of Presentation
      豊橋
    • Year and Date
      2010-11-07
    • Related Report
      2010 Annual Research Report 2010 Final Research Report
  • [Presentation] ルイス酸触媒カルボニルイリド付加環化反応を経由する高立体選択的三成分連結反応の開発2010

    • Author(s)
      菅博幸
    • Organizer
      第40回複素環化学討論会
    • Place of Presentation
      仙台
    • Year and Date
      2010-10-15
    • Related Report
      2010 Annual Research Report 2010 Final Research Report
  • [Presentation] 1-ジアゾ-2,5-ペンタンジオン誘導体より発生させたカルボニルイリドの逆電子要請型不斉付加環化反応2010

    • Author(s)
      菅博幸
    • Organizer
      第40回複環化学討論会
    • Place of Presentation
      仙台
    • Year and Date
      2010-10-14
    • Related Report
      2010 Final Research Report
  • [Presentation] 1-ジアゾ-2,5-ペンタンジオン誘導体より発生させたカルボニルイリドの逆電子要請型不斉付加環化反応2010

    • Author(s)
      菅博幸
    • Organizer
      第40回複素環化学討論会
    • Place of Presentation
      仙台
    • Year and Date
      2010-10-14
    • Related Report
      2010 Annual Research Report
  • [Presentation] N-ジアゾアセチル-2-ピロリジノンを前駆体とするカルボニルイリドのキラルルイス酸触媒不斉付加環化反応とその合成化学的応用2010

    • Author(s)
      菅博幸
    • Organizer
      日本化学会第90春季年会
    • Place of Presentation
      大阪
    • Year and Date
      2010-03-27
    • Related Report
      2010 Final Research Report
  • [Presentation] Nジアゾアセチル-2-ピロリジノンを前駆体とするカルボニルイリドのキラルルイス酸触媒不斉付加環化反応とその合成化学的応用2010

    • Author(s)
      菅博幸
    • Organizer
      日本化学会第90春季年会
    • Place of Presentation
      大阪
    • Year and Date
      2010-03-27
    • Related Report
      2009 Annual Research Report
  • [Presentation] ジアゾイミン誘導体より発生させた環状アゾメチンイリドのキラルビナフチルジイミン-及びジアミン-金属錯体を触媒とする不斉1,3-双極性付加環化反応2010

    • Author(s)
      菅博幸
    • Organizer
      日本化学会第90春季年会
    • Place of Presentation
      大阪
    • Year and Date
      2010-03-27
    • Related Report
      2009 Annual Research Report
  • [Presentation] N-ジアゾアセチル-2-ピロリジノンより発生させたカルボニルイリドとアルケン酸誘導体とのキラルルイス酸触媒不斉付加環化反応2009

    • Author(s)
      菅博幸
    • Organizer
      第39回複素環化学討論会
    • Place of Presentation
      千葉
    • Year and Date
      2009-10-15
    • Related Report
      2010 Final Research Report
  • [Presentation] Nジアゾアセチル-2-ピロリジノンより発生させたカルボニルイリドとアルケン酸誘導体とのキラルルイス酸触媒不斉付加環化反応2009

    • Author(s)
      菅博幸
    • Organizer
      第39回複素環化学討論会
    • Place of Presentation
      千葉
    • Year and Date
      2009-10-15
    • Related Report
      2009 Annual Research Report
  • [Presentation] ジアゾイミン誘導体より発生させた環状アゾメチンイリドと2-アクリロイル-3-ピラゾリジノン類とのルイス酸触媒不斉1,3-双極性付加環化反応2009

    • Author(s)
      菅博幸
    • Organizer
      第39回複素環化学討論会
    • Place of Presentation
      千葉
    • Year and Date
      2009-10-15
    • Related Report
      2009 Annual Research Report
  • [Presentation] Chiral Lewis acid catalyzed asymmetric cycloaddition reactions of cyclic ylides generated from diazocarbonyl compounds2009

    • Author(s)
      菅博幸
    • Organizer
      22nd International Congress on Heterocyclic Chemistry
    • Place of Presentation
      St.Johns(Canada)
    • Year and Date
      2009-08-03
    • Related Report
      2010 Final Research Report
  • [Presentation] Chiral Lewis acid catalyzed asymmetric cycloaddition reactions of cyclicylides generated from diazocarbonyl compounds2009

    • Author(s)
      菅博幸
    • Organizer
      22nd International Congress on Heterocyclic Chemistry
    • Place of Presentation
      St.Johns(Canada)
    • Year and Date
      2009-08-03
    • Related Report
      2009 Annual Research Report
  • [Presentation] キラルルイス酸存在下における環状カルボニルイリドと種々のオレフィン類との不斉付加環化反応-オレフィン基質に対する適応範囲2009

    • Author(s)
      菅博幸
    • Organizer
      日本化学会第89春季年会
    • Place of Presentation
      船橋
    • Year and Date
      2009-03-29
    • Related Report
      2010 Final Research Report 2008 Annual Research Report
  • [Presentation] ジアゾ酢酸エステルと2-(2-アルケノイル)-3-ピラゾリジノン誘導体とのビナフチルジイミン-Ni(II)触媒不斉1, 3-双極性付加環化反応2009

    • Author(s)
      菅博幸
    • Organizer
      日本化学会第89春季年会
    • Place of Presentation
      船橋
    • Year and Date
      2009-03-29
    • Related Report
      2008 Annual Research Report
  • [Presentation] カルボニルイリドと電子過剰オレフィンとのキラルルイス酸触媒不斉付加環化反応-基質一般性の検討2008

    • Author(s)
      菅博幸
    • Organizer
      第38回複素環化学討論会
    • Place of Presentation
      福山
    • Year and Date
      2008-11-22
    • Related Report
      2010 Final Research Report 2008 Annual Research Report
  • [Presentation] ビナフチルジイミン-Ni(II)触媒を用いるニトリルオキシドと2-(2-アルケノイル)-3-ピラゾリジノン誘導体との不斉付加環化反応2008

    • Author(s)
      菅博幸
    • Organizer
      第38回複素環化学討論会
    • Place of Presentation
      福山
    • Year and Date
      2008-11-22
    • Related Report
      2008 Annual Research Report
  • [Book] Heterocyclic Supramolecules II Series : Topics in Heterocyclic Chemistry,(Matsumoto, Kiyoshi; Hayashi, Naoto (Eds.)) Vol.18, (全 157 p.のうち 36 p.分担執筆)2009

    • Author(s)
      Hiroyuki SUGA, その他9名
    • Publisher
      Springer
    • Related Report
      2010 Final Research Report
  • [Remarks] ホームページ等

    • URL

      http://wwweng.cs.shinshu-u.ac.jp/CHEM/lab_suga/framepage5.html

    • Related Report
      2010 Final Research Report

URL: 

Published: 2008-04-01   Modified: 2018-03-28  

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