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Stereocontrol of Chiral Carbanions in Tandem Reactions

Research Project

Project/Area Number 19390006
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Chemical pharmacy
Research InstitutionHiroshima University

Principal Investigator

TAKEDA Kei  Hiroshima University, 大学院・医歯薬学総合研究科, 教授 (30135032)

Co-Investigator(Kenkyū-buntansha) SASAKI Michiko  広島大学, 大学院・医歯薬学総合研究科, 助教 (30379888)
Project Period (FY) 2007 – 2009
Project Status Completed (Fiscal Year 2009)
Budget Amount *help
¥18,720,000 (Direct Cost: ¥14,400,000、Indirect Cost: ¥4,320,000)
Fiscal Year 2009: ¥5,460,000 (Direct Cost: ¥4,200,000、Indirect Cost: ¥1,260,000)
Fiscal Year 2008: ¥6,110,000 (Direct Cost: ¥4,700,000、Indirect Cost: ¥1,410,000)
Fiscal Year 2007: ¥7,150,000 (Direct Cost: ¥5,500,000、Indirect Cost: ¥1,650,000)
Keywords不斉転写 / キラルカルバニオン / [2,3]-Wittig転位 / 不斉反応 / 転位反応 / [2, 3]-Wittig転位 / 光学活性アレン
Research Abstract

(1) We have found that the extent of chirality transfer in [2,3]-Wittig rearrangement employing a chiral β-substituted allyl benzyl carbanion can be used as a tool for evalulation of the effect of substituents on the configurational stability of a chiral carbanion through a double bond.
(2) Treatment of (R, Z)-3-(tert-butyldimethylsilyl)-1-cyano-3-hydroxyprop-1-enyl carbamate with a catalytic amount of a base afforded (S, E)-3-(tert-butyldimethylsilyloxy)-1-cyanoallyl diisopropyl- carbamate, showing that S_E2'-type reaction of allylsilicates proceeds in an anti-mode fashion. The overall process is equivalent to trapping of an enantioenriched C-chiral carbanion at α-position of nitrile group in up to 77% ee.

Report

(4 results)
  • 2009 Annual Research Report   Final Research Report ( PDF )
  • 2008 Annual Research Report
  • 2007 Annual Research Report
  • Research Products

    (45 results)

All 2010 2009 2008 2007 Other

All Journal Article (13 results) (of which Peer Reviewed: 13 results) Presentation (27 results) Remarks (5 results)

  • [Journal Article] [2, 3]-Wittig Rearrangement of Enantiomeri-cally Enriched 3-Substituted 1-Propenyloxy-1-phenyl-2-propen-1-yl Carbanions: Effect of Heteroatoms and Conjugating Groups on Planarization of an a-Oxy-Benzylcarbanion Through a Double Bond2009

    • Author(s)
      Michiko Sasaki, Hidaka Ikemoto, Masatoshi Kawahata, Kentaro Yamaguchi, Kei Takeda
    • Journal Title

      Chem. Eur. J 15

      Pages: 4663-4666

    • Related Report
      2009 Final Research Report
    • Peer Reviewed
  • [Journal Article] Stereoselective Brook Rearrangement-Medi-ated SE2' Protonation of a-Hydroxy Allyl Silanes2009

    • Author(s)
      Michiko Sasaki, Yuri Shirakawa, Masatoshi Kawahata, Kentaro Yamaguchi, Kei Takeda
    • Journal Title

      Chem. Eur. J 15

      Pages: 3363-3366

    • Related Report
      2009 Final Research Report
    • Peer Reviewed
  • [Journal Article] [2,3]-Wittig Rearrangement of Enantiomerically Enriched 3-Substituted 1-Propenyloxy-1-phenyl-2-propen-1-yl Carbanions : Effect of Heteroatoms and Conjugating Groups on Planarization of an α-Oxy-Benzylcarbanion Through a Double Bond2009

    • Author(s)
      Michiko Sasaki
    • Journal Title

      Chemistry-A European Journal 15

      Pages: 4663-4666

    • Related Report
      2009 Annual Research Report
    • Peer Reviewed
  • [Journal Article] One-pot Tandem Concise Synthesis of Indoles and Isoquinolines from Amides2009

    • Author(s)
      Noriko Okamoto
    • Journal Title

      Angewandte Chemie International Edition 48

      Pages: 9693-9696

    • Related Report
      2009 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Development of Epoxysilane Rearrangement and its Application to Chirality Transfer2009

    • Author(s)
      Michiko Sasaki
    • Journal Title

      Heterocycles 78

      Pages: 2919-2941

    • NAID

      40016842003

    • Related Report
      2009 Annual Research Report
    • Peer Reviewed
  • [Journal Article] One-pot Concise Syntheses of Benzimidazo[2,1-a]isoquinolines by Microwave-Accelerated Tandem Process2009

    • Author(s)
      Noriko Okamoto
    • Journal Title

      Teterahedron Letters 50

      Pages: 4167-4169

    • Related Report
      2009 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Design and Synthesis of A Stable Supramolecular Trigonal Prism Formed by the Self-Assembly of A Linear Tetrakis(Zn^<2+>-cyclen) Complex and Trianionic Trithiocyanuric Acid in Aqueous Solution and Its Complexation with DNA (Cyclen=1,4,7,10-Tetraazacyclododecane)2009

    • Author(s)
      Mohd Zulkefeli
    • Journal Title

      Inorganic Chemistry 48

      Pages: 9567-9578

    • Related Report
      2009 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Development of Cyclic Hydrazine and Hydrazine Type Organocatalyst -Mechanistic Aspects of Cyclic Hydrazine/Hydrazide-Catalyzed Diels-Alder Reactions2009

    • Author(s)
      Ichiro Suzuki
    • Journal Title

      Heterocycles 79

      Pages: 851-863

    • Related Report
      2009 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Stereoselective Brook Rearrangement-Mediated S_E2' Protonation of a-Hydroxy Allyl Silanes2009

    • Author(s)
      Michiko Sasaki
    • Journal Title

      Chemistry -A European Journal

      Pages: 3363-3366

    • Related Report
      2008 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Chirality Transfer from Epoxide to Carbanion: Base-Induced Alkylation of O-Carbamoyl Cyanohydrins of b-Silyl-a, b-epoxyaldehyde2008

    • Author(s)
      Michiko Sasaki, Eiji Kawanishi, Yuri Shirakawa, Masatoshi Kawahata, Hyuma Masu, Kentaro Yamaguchi, Kei Takeda
    • Journal Title

      Eur. J. Org. Chem

      Pages: 3061-3064

    • Related Report
      2009 Final Research Report
    • Peer Reviewed
  • [Journal Article] Chirality Transfer from Epoxide to Carbanion : Base-Induced Alkylation of O-Carbamoyl Cyanohydrins of β-Silvl-a, β-epoxyaldehyde2008

    • Author(s)
      Michiko Sasaki
    • Journal Title

      European Journal of Organic Chemistry

      Pages: 3061-3064

    • Related Report
      2008 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Diastereoselective Brook Rearrangement-Mediated [3+4]Annulation : Application to a Formal Synthesis of (+)-Laurallene2008

    • Author(s)
      Michiko Sasaki
    • Journal Title

      Organic Letters 10

      Pages: 1803-1806

    • Related Report
      2008 Annual Research Report
    • Peer Reviewed
  • [Journal Article] 連続的炭素-炭素結合形成反応を機軸とする新規合成反応の開発研究2007

    • Author(s)
      武田 敬
    • Journal Title

      薬学雑誌(受賞記念招待執筆) 127

      Pages: 1399-1418

    • NAID

      110006380724

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Presentation] Brook 転位を利用するシロキシアレンのエナンチオ選択的合成法の開発2010

    • Author(s)
      佐々木道子
    • Organizer
      日本薬学会第130年会
    • Place of Presentation
      岡山市
    • Year and Date
      2010-03-29
    • Related Report
      2009 Annual Research Report
  • [Presentation] キラルカルバニオンの立体化学的安定性に対する溶媒効果2010

    • Author(s)
      池本陽峰
    • Organizer
      日本薬学会第130年会
    • Place of Presentation
      岡山市
    • Year and Date
      2010-03-29
    • Related Report
      2009 Annual Research Report
  • [Presentation] ジアミノイミダゾリジノン型有機触媒を用いた不斉1,3-双極子付加環化反応の開発2010

    • Author(s)
      鈴木一郎
    • Organizer
      日本薬学会第130年会
    • Place of Presentation
      岡山市
    • Year and Date
      2010-03-28
    • Related Report
      2009 Annual Research Report
  • [Presentation] キラルジアミノイミダゾリジノン誘導体を触媒として用いる不斉 Diels-Alder 反応2010

    • Author(s)
      鈴木一郎
    • Organizer
      日本薬学会第130年会
    • Place of Presentation
      岡山市
    • Year and Date
      2010-03-28
    • Related Report
      2009 Annual Research Report
  • [Presentation] [3+4] アニュレーションを用いる(+)-Prelaureatin の合成研究2009

    • Author(s)
      佐々木道子
    • Organizer
      第35回反応と合成の進歩シンポジウム
    • Place of Presentation
      金沢市
    • Year and Date
      2009-11-17
    • Related Report
      2009 Annual Research Report
  • [Presentation] 有機触媒を用いた Biginelli 反応の開発2009

    • Author(s)
      鈴木一郎
    • Organizer
      第35回反応と合成の進歩シンポジウム
    • Place of Presentation
      金沢市
    • Year and Date
      2009-11-16
    • Related Report
      2009 Annual Research Report
  • [Presentation] アミドの Hofmann 型転位を利用する環状ビスインドール合成2009

    • Author(s)
      岡本典子
    • Organizer
      第35回反応と合成の進歩シンポジウム
    • Place of Presentation
      金沢市
    • Year and Date
      2009-11-16
    • Related Report
      2009 Annual Research Report
  • [Presentation] Effects of Solvents on the Trapping of Chiral Carbanions by [2,3]-Wittig Rearrangement2009

    • Author(s)
      池本陽峰
    • Organizer
      11th International Kyoto Conference on New Aspects of Organic Chemistry
    • Place of Presentation
      京都市
    • Year and Date
      2009-11-10
    • Related Report
      2009 Annual Research Report
  • [Presentation] Hydradize-Catalyzed Enantioselective Diels-Alder Reactions2009

    • Author(s)
      鈴木一郎
    • Organizer
      11th International Kyoto Conference on New Aspects of Organic Chemistry
    • Place of Presentation
      京都市
    • Year and Date
      2009-11-10
    • Related Report
      2009 Annual Research Report
  • [Presentation] [3+4] アニュレーションを利用する(+)-Prelaureatin の合成研究2009

    • Author(s)
      佐々木道子
    • Organizer
      第48回日本薬学会・日本病院薬剤師会中国四国支部学術大会
    • Place of Presentation
      徳島市
    • Year and Date
      2009-11-07
    • Related Report
      2009 Annual Research Report
  • [Presentation] Brook 転位を利用する光学活性シロキシアレンの合成2009

    • Author(s)
      佐々木道子
    • Organizer
      第48回日本薬学会・日本病院薬剤師会中国四国支部学術大会
    • Place of Presentation
      徳島市
    • Year and Date
      2009-11-07
    • Related Report
      2009 Annual Research Report
  • [Presentation] ヒドラジド型有機触媒を用いた不斉1,3-双極子付加環化反応の開発2009

    • Author(s)
      安藤雅史
    • Organizer
      第48回日本薬学会・日本病院薬剤師会中国四国支部学術大会
    • Place of Presentation
      徳島市
    • Year and Date
      2009-11-07
    • Related Report
      2009 Annual Research Report
  • [Presentation] 新規ヒドラジド触媒を用いる不斉 Diels-Alder 反応2009

    • Author(s)
      平田愛
    • Organizer
      第48回日本薬学会・日本病院薬剤師会中国四国支部学術大会
    • Place of Presentation
      徳島市
    • Year and Date
      2009-11-07
    • Related Report
      2009 Annual Research Report
  • [Presentation] [2,3]-Wittig 転位を利用するキラルカルバニオンの立体化学的安定性の評価2009

    • Author(s)
      池本陽峰
    • Organizer
      第7回次世代を担う有機化学シンポジウム
    • Place of Presentation
      大阪市
    • Year and Date
      2009-07-23
    • Related Report
      2009 Annual Research Report
  • [Presentation] Development of New Synthetic Methodology Featuring Tandem-Bond Forming Process and Their Application to the Total□ Synthesis of Natural Products2009

    • Author(s)
      Kei Takeda
    • Organizer
      Organic Seminar, Department of Chemistry University of Rochester
    • Place of Presentation
      Rochester, NY, USA
    • Year and Date
      2009-06-16
    • Related Report
      2009 Annual Research Report
  • [Presentation] Development of New Synthetic Methodology Featuring Tandem-Bond Forming Process and Their Application to the Total□ Synthesis of Natural Products2009

    • Author(s)
      Kei Takeda
    • Organizer
      Organic Chemistry Seminar, Department of Chemistry, University of Toronto
    • Place of Presentation
      Toronto, ON, Canada
    • Year and Date
      2009-06-15
    • Related Report
      2009 Annual Research Report
  • [Presentation] Trapping of Chiral Carbanions by [2, 3]- Wittig Rearrangement: Effect of Hetero- atoms and Conjugating Groups2009

    • Author(s)
      Hidaka Ikemoto, Michiko Sasaki, Kei Takeda
    • Organizer
      41st National Organic Chemistry Symposium
    • Place of Presentation
      Boulder, CO, USA
    • Year and Date
      2009-06-08
    • Related Report
      2009 Final Research Report
  • [Presentation] Use of a Brook Rearrangement-Mediated [3+4] Annulation Toward the Total Synthesis of (+)-Prelaureatin2009

    • Author(s)
      佐々木道子
    • Organizer
      41st National Organic Chemistry Symposium
    • Place of Presentation
      Boulder, CO, USA
    • Year and Date
      2009-06-08
    • Related Report
      2009 Annual Research Report
  • [Presentation] Trapping of Chiral Carbanions by [2,3]-Wittig Rearrangement : Effect of Heteroatoms and Conjugating Groups2009

    • Author(s)
      池本陽峰
    • Organizer
      41st National Organic Chemistry Symposium
    • Place of Presentation
      Boulder, CO, USA
    • Year and Date
      2009-06-08
    • Related Report
      2009 Annual Research Report
  • [Presentation] 光学活性a-ヒドロキシアリルシランのS_E2'型反応を利用する不斉転写2009

    • Author(s)
      佐々木道子
    • Organizer
      日本薬学会第129年会
    • Place of Presentation
      京都市
    • Year and Date
      2009-03-26
    • Related Report
      2008 Annual Research Report
  • [Presentation] [2, 3]-Wittig転位を利用するキラルカルバニオンの立体化学的安定性の評価2009

    • Author(s)
      佐々木道子
    • Organizer
      日本薬学会第129年会
    • Place of Presentation
      京都市
    • Year and Date
      2009-03-26
    • Related Report
      2008 Annual Research Report
  • [Presentation] [3+4]アニュレーシヨンを用いる(+)-Prelaureatinの合成研究2008

    • Author(s)
      佐々木道子
    • Organizer
      第38回複素環化学討論会
    • Place of Presentation
      福山市
    • Year and Date
      2008-11-22
    • Related Report
      2008 Annual Research Report
  • [Presentation] [2, 3]-Wittig転位を利用するキラルカルバニオンの立体化学的安定性の比較2008

    • Author(s)
      佐々木道子
    • Organizer
      第34回反応と合成の進歩シンポジウム
    • Place of Presentation
      京都市
    • Year and Date
      2008-11-04
    • Related Report
      2008 Annual Research Report
  • [Presentation] Trapping of Chiral Carbanions by [2, 3]-Wittig Rearrangement2008

    • Author(s)
      Michiko Sasaki
    • Organizer
      The 236th National Meeting of the American Chemical Society
    • Place of Presentation
      Philadelphia, PA, USA
    • Year and Date
      2008-08-19
    • Related Report
      2008 Annual Research Report
  • [Presentation] Chirality Transfer from Epoxide to Carbanion : Base-induced Alkylation of O-Carbamoyl Cyanohydrins of β-Silyl-a. β-epoxyaldehvde2008

    • Author(s)
      Michiko Sasaki
    • Organizer
      The 236th National Meeting of the American Chemical Society
    • Place of Presentation
      Philadelphia, PA, USA
    • Year and Date
      2008-08-19
    • Related Report
      2008 Annual Research Report
  • [Presentation] Trapping of Chiral Carbanions by [2, 3]-Wittig Rearrangement2008

    • Author(s)
      Michiko Sasaki, Hidaka Ikemoto, Mariko Higashi, Kei Takeda
    • Organizer
      The 236th National Meeting of the American Chemical Society (Sci-Mix)
    • Place of Presentation
      Philadelphia, PA, USA
    • Year and Date
      2008-08-18
    • Related Report
      2009 Final Research Report 2008 Annual Research Report
  • [Presentation] Chirality Transfer from Epoxide to α-Nitrile Allylic Carbanion via Epoxysilane Rearrangement2007

    • Author(s)
      Michiko Sasaki
    • Organizer
      40th National Oreanic Chemistry Symposium
    • Place of Presentation
      Duke University, Durham, NC, USA
    • Year and Date
      2007-06-06
    • Related Report
      2007 Annual Research Report
  • [Remarks]

    • URL

      http://home.hiroshima-u.ac.jp/takedake/

    • Related Report
      2009 Final Research Report
  • [Remarks]

    • URL

      http://home.hiroshima-u.ac.jp/takedake/index-e.html

    • Related Report
      2009 Final Research Report
  • [Remarks]

    • URL

      http://home.hiroshima-u.ac.jp/takedake/

    • Related Report
      2009 Annual Research Report
  • [Remarks]

    • URL

      http://home.hiroshima-u.ac.jp/takedake/index-e.html

    • Related Report
      2009 Annual Research Report
  • [Remarks]

    • URL

      http://home.hiroshima-u.ac.jp/takedake/

    • Related Report
      2008 Annual Research Report

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

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