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Generation of multifunctionalized nucleophilic carbenes

Research Project

Project/Area Number 22790011
Research Category

Grant-in-Aid for Young Scientists (B)

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

Principal Investigator

SASAKI Michiko  広島大学, 大学院・医歯薬保健学研究院, 准教授 (30379888)

Project Period (FY) 2010 – 2012
Project Status Completed (Fiscal Year 2012)
Budget Amount *help
¥4,030,000 (Direct Cost: ¥3,100,000、Indirect Cost: ¥930,000)
Fiscal Year 2012: ¥1,170,000 (Direct Cost: ¥900,000、Indirect Cost: ¥270,000)
Fiscal Year 2011: ¥1,170,000 (Direct Cost: ¥900,000、Indirect Cost: ¥270,000)
Fiscal Year 2010: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
Keywords有機合成 / 合成化学 / エポキシシラン / カルベン / 有機化学 / 連続反応
Research Abstract

With the aim of developing a method that allows the generation of nucleophilic carbenes at a cryogenic temperature, we focused on an iminium salt derived from β-silyl-α,β-epoxyaldehydes, which can potentially generate a nucleophilic carbene via deprotonation of a proton on an iminium carbon atom, ring-opening of epoxide and Brook rearrangement of the resulting α-silyl alkoxide. We devised a method for the preparation of the substrates and found that some structural modification of the substrates is required to successfully generate a nucleophilc carbene. During the attempt, we also found that 1,n-dipole (n ≠3), a new class of synthons, can serve important intermediates in the synthesis of complex molecules.

Report

(4 results)
  • 2012 Annual Research Report   Final Research Report ( PDF )
  • 2011 Annual Research Report
  • 2010 Annual Research Report
  • Research Products

    (61 results)

All 2013 2012 2011 2010 Other

All Journal Article (16 results) (of which Peer Reviewed: 16 results) Presentation (39 results) Remarks (6 results)

  • [Journal Article] Chirality Transfer in Brook Rearrangement-Mediated SE2' Solvolytic Protonation and Its Use in Estimation of the Propensity for Racemization of the α-Lithiocarbanions of the Substituents2013

    • Author(s)
      Michiko Sasaki, Misato Fujiwara, Yuri Kotomori, Masatoshi Kawahata, Kentaro Yamaguchi, Kei Takeda
    • Volume
      69
    • Pages
      5823-5828
    • Related Report
      2012 Final Research Report
    • Peer Reviewed
  • [Journal Article] 立体化学的に不安定なキラルカルバニオンの合成化学への展開2013

    • Author(s)
      佐々木道子,武田 敬
    • Journal Title

      有機合成化学協会誌

      Volume: 71 Pages: 136-148

    • NAID

      10031148205

    • Related Report
      2012 Annual Research Report 2012 Final Research Report
    • Peer Reviewed
  • [Journal Article] Synthetic Potential of Configurationally Unstable Chiral Carbanions2012

    • Author(s)
      Michiko Sasaki, Kei Takeda
    • Journal Title

      SYNLETT (ACCOUNT, invited)

      Volume: 23 Pages: 2153-2164

    • NAID

      10031148205

    • Related Report
      2012 Final Research Report
    • Peer Reviewed
  • [Journal Article] Enantioselective Trapping of an α-Chiral Carbanion of Acyclic Nitrile by a Carbon Electrophile2012

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

      Chem. Commun

      Volume: 48 Pages: 2897-2899

    • Related Report
      2012 Final Research Report
    • Peer Reviewed
  • [Journal Article] DISCUSSION ADDENDUM FOR: [3 + 4] Annulation Using a [β-(Trimethylsilyl)acryloyl]silane and the Lithium Enolate of an α,β-Unsaturated Methyl Ketone: (1R,6S,7S)-4-(tert-Butyldimethylsiloxy)-6-(trimethylsilyl)bicyclo[5.4.0]undec-4-en-2-one2012

    • Author(s)
      Kei Takeda, Michiko Sasaki
    • Journal Title

      Org. Synth

      Volume: 89 Pages: 267-273

    • Related Report
      2012 Final Research Report
    • Peer Reviewed
  • [Journal Article] Enantioselective Trapping of an a-Chiral Carbanion of Acyclic Nitrile by a Carbon Electrophile2012

    • Author(s)
      Michiko Sasaki
    • Journal Title

      Chemical Communications

      Volume: 48 Issue: 23 Pages: 2897-2899

    • DOI

      10.1039/c2cc00082b

    • Related Report
      2012 Annual Research Report 2011 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthetic Potential of Configurationally Unstable Chiral Carbanions2012

    • Author(s)
      Michiko Sasaki
    • Journal Title

      Synlett

      Volume: 23 Issue: 15 Pages: 2153-2164

    • DOI

      10.1055/s-0031-1290440

    • NAID

      10031148205

    • Related Report
      2012 Annual Research Report
    • Peer Reviewed
  • [Journal Article] DISCUSSION ADDENDUM FOR : [3+4] Annulation Using a [β-(Trimethylsilyl) acryloyl] silane and the Lithium Enolate of an α,β-Unsaturated Methyl Ketone : (1R,6S,7S)-4-(tert-Butyldimethylsiloxy)-6-(trimethylsilyl) bicyclo[5.4.0] undec-4-en-2-one2012

    • Author(s)
      Kei Takeda
    • Journal Title

      Organic Syntheses

      Volume: 89 Pages: 267-273

    • Related Report
      2011 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Steric Course of the Electrophilc Substitution of a Lithiocarbanion Generated from (S,E)-1-Phenylbut-2-en-1-yl Diisopropylcarbamate and Solvent Effects2011

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

      Eur. J. Org. Chem

      Pages: 6553-6557

    • Related Report
      2012 Final Research Report
    • Peer Reviewed
  • [Journal Article] Enantioselective Synthesis of Siloxyallenes from Alkynoyl Silanes by Reduction and a Brook Rearrangement and Their Subsequent Trapping in a [4+2] Cycloaddition2011

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

      Angew. Chem. Int. Ed

      Volume: 50 Pages: 6375-6378

    • Related Report
      2012 Final Research Report
    • Peer Reviewed
  • [Journal Article] Steric Course of the Electrophilc Substitution of a Lithiocarbanion Generated from (S,E)-1-Phenylbut-2-en-1-yl Diisopropylcarbamate and Solvent Effects2011

    • Author(s)
      Hidaka Ikemoto
    • Journal Title

      European Journal of Organic Chemistry

      Volume: 2011 Issue: 32 Pages: 6553-6557

    • DOI

      10.1002/ejoc.201100970

    • Related Report
      2011 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Enantioselective Synthesis of Siloxyallenes from Alkynoyl Silanes by Reduction and a Brook Rearrangement and Their Subsequent Trapping in a [4+2] Cycloaddition2011

    • Author(s)
      Michiko Sasaki
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 50 Issue: 28 Pages: 6375-6378

    • DOI

      10.1002/anie.201102430

    • Related Report
      2011 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Solvent Effects on the Steric Course of [2,3]-Wittig Rearrangement of (S,E)-(3-(allyloxy)prop-1-ene-1,3-diyl)dibenzene and Its Derivatives2010

    • Author(s)
      Hidaka Ikemoto, Michiko Sasaki, Kei Takeda
    • Journal Title

      Eur. J. Org. Chem

      Pages: 6643-6650

    • Related Report
      2012 Final Research Report
    • Peer Reviewed
  • [Journal Article] Formal Total Syntheses of (+)-Prelaureatin and (+)-Laurallene by Diastereoselective Brook Rearrangement-Mediated [3 + 4] Annulation2010

    • Author(s)
      Michiko Sasaki, Kazuhisa Oyamada, Kei Takeda
    • Journal Title

      J. Org. Chem

      Volume: 75 Pages: 3941-3943

    • Related Report
      2012 Final Research Report
    • Peer Reviewed
  • [Journal Article] Solvent Effects on the Steric Course of[2,3]-Wittig Rearrangement of(S,E)-(3-(allyloxy)prop-1-ene-1,3-diyl)dibenzene and Its Derivatives2010

    • Author(s)
      Hidaka Ikemoto
    • Journal Title

      European Journal of Organic Chemistry

      Pages: 6643-6650

    • Related Report
      2010 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Formal Total Syntheses of (+)-Prelaureatin and (+)-Laurallene by Diastereoselective Brook Rearrangement-Mediated[3+4]Annulation2010

    • Author(s)
      Michiko Sasaki
    • Journal Title

      The Journal of Organic Chemistry

      Volume: 75 Pages: 3941-3943

    • Related Report
      2010 Annual Research Report
    • Peer Reviewed
  • [Presentation] Evaluation of the configurational stability of carbanions next to conjugating electron-withdrawing groups2013

    • Author(s)
      Michiko Sasaki
    • Organizer
      19th International Conference on Organic Synthesis
    • Place of Presentation
      Melbourne, Australia
    • Related Report
      2012 Annual Research Report 2012 Final Research Report
  • [Presentation] Enantioselective trapping of an α-chiral carbanion of acyclic nitrile by a carbon electrophile2013

    • Author(s)
      Michiko Sasaki
    • Organizer
      19th International Conference on Organic Synthesis
    • Place of Presentation
      Melbourne, Australia
    • Related Report
      2012 Annual Research Report 2012 Final Research Report
  • [Presentation] ウレイド基のキレーションを利用するキラルα-ニトリルカルバニオンの発生と求電子剤との反応2013

    • Author(s)
      佐々木 道子
    • Organizer
      日本薬学会第133年会
    • Place of Presentation
      横浜
    • Related Report
      2012 Annual Research Report
  • [Presentation] 光学活性α-ヒドロキシアリルシランの異性化反応における不斉転写の機構2013

    • Author(s)
      佐々木 道子
    • Organizer
      日本薬学会第133年会
    • Place of Presentation
      横浜
    • Related Report
      2012 Annual Research Report
  • [Presentation] キラルリチウムアミドを利用するイミンの不斉還元反応2013

    • Author(s)
      佐々木 道子
    • Organizer
      日本薬学会第133年会
    • Place of Presentation
      横浜
    • Related Report
      2012 Annual Research Report
  • [Presentation] エポキシシラン転位を利用するシリルケテンイミンの発生とその反応2013

    • Author(s)
      佐々木 道子
    • Organizer
      日本薬学会第133年会
    • Place of Presentation
      横浜
    • Related Report
      2012 Annual Research Report
  • [Presentation] β位に電子求引基を有するシクロプロピルアシルシランと求核剤との反応2012

    • Author(s)
      佐々木道子
    • Organizer
      日本薬学会第132年会
    • Place of Presentation
      札幌
    • Year and Date
      2012-03-30
    • Related Report
      2011 Annual Research Report
  • [Presentation] キラルα-ニトリルカルバニオンの求電子剤による捕捉(2)2012

    • Author(s)
      佐々木道子
    • Organizer
      日本薬学会第132年会
    • Place of Presentation
      札幌
    • Year and Date
      2012-03-30
    • Related Report
      2011 Annual Research Report
  • [Presentation] キラルリチウムアミドによる還元を鍵反応とするアレン類のエナンチオ選択的合成2012

    • Author(s)
      佐々木道子
    • Organizer
      日本薬学会第132年会
    • Place of Presentation
      札幌
    • Year and Date
      2012-03-30
    • Related Report
      2011 Annual Research Report
  • [Presentation] 共役性電子求引基およびヘテロ原子置換基に隣接するキラルカルバニオンのラセミ化傾向の比較2012

    • Author(s)
      佐々木 道子
    • Organizer
      第38回反応と合成の進歩シンポジウム
    • Place of Presentation
      東京
    • Related Report
      2012 Annual Research Report
  • [Presentation] カルバモイル基により立体化学的に安定化されたキラルα-ニトリルカルバニオンの捕捉2012

    • Author(s)
      佐々木 道子
    • Organizer
      第102回有機合成シンポジウム
    • Place of Presentation
      東京
    • Related Report
      2012 Annual Research Report
  • [Presentation] Mechanistic Study of Stereoselective SE2' Protonation of a-Hydroxy Allyl Silanes2012

    • Author(s)
      Michiko Sasaki
    • Organizer
      12th International Kyoto Conference on New Aspects of Organic Chemistry
    • Place of Presentation
      Kyoto
    • Related Report
      2012 Annual Research Report
  • [Presentation] Enantioselective Trapping of Chiral a-Nitrile Carbanions2012

    • Author(s)
      Michiko Sasaki
    • Organizer
      12th International Kyoto Conference on New Aspects of Organic Chemistry
    • Place of Presentation
      Kyoto
    • Related Report
      2012 Annual Research Report
  • [Presentation] Enantioselective Synthesis of Allenes via Tandem Enantioselective Reduction/Brook Rearrangement2011

    • Author(s)
      佐々木道子
    • Organizer
      10th International Symposium on Organic Reactions
    • Place of Presentation
      横浜
    • Year and Date
      2011-11-23
    • Related Report
      2011 Annual Research Report
  • [Presentation] 共役性電子求引性基に隣接するキラルカルバニオンの立体化学的安定性の評価(2)2011

    • Author(s)
      佐々木道子
    • Organizer
      第50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
      高松
    • Year and Date
      2011-11-12
    • Related Report
      2011 Annual Research Report
  • [Presentation] 脱プロトン化によるキラルα-ニトリルカルバニオンの発生と捕捉2011

    • Author(s)
      佐々木道子
    • Organizer
      第100回有機合成シンポジウム
    • Place of Presentation
      東京
    • Year and Date
      2011-11-11
    • Related Report
      2011 Annual Research Report
  • [Presentation] アリルベンジルリチオカルバニオンに対する求電子置換反応の立体化学-求電子剤と溶媒の効果-2011

    • Author(s)
      佐々木道子
    • Organizer
      第100回有機合成シンポジウム
    • Place of Presentation
      東京
    • Year and Date
      2011-11-10
    • Related Report
      2011 Annual Research Report
  • [Presentation] 光学活性シロキシアレン類の合成と[4+2]型環化付加による捕捉2011

    • Author(s)
      佐々木道子
    • Organizer
      第37回反応と合成の進歩シンポジウム
    • Place of Presentation
      徳島
    • Year and Date
      2011-11-08
    • Related Report
      2011 Annual Research Report
  • [Presentation] Chiral Organolithiums Next to a Conjugative Electron-Withdrawing Group : Their Configurational Stability and Enantioselective Trapping by an Electrophile2011

    • Author(s)
      Michiko Sasaki
    • Organizer
      The 242nd National Meeting of the American Chemical Society
    • Place of Presentation
      Denver, Colorado, USA
    • Year and Date
      2011-08-31
    • Related Report
      2011 Annual Research Report
  • [Presentation] Chiral Organolithiums Next to a Conjugative Electron-Withdrawing Group : Their Configurational Stability and Enantioselective Trapping by an Electrophile2011

    • Author(s)
      Michiko Sasaki
    • Organizer
      The 242nd National Meeting of the American Chemical Society (Sci Mix)
    • Place of Presentation
      Denver, CO, USA
    • Year and Date
      2011-08-29
    • Related Report
      2011 Annual Research Report
  • [Presentation] Enantioselective Synthesis of Siloxyallenes from Alkynoylsilanes Via Tandem Enantioselective Reduction/Brook Rearrangement and Their Subsequent Trapping by [4+2] Cycloaddition2011

    • Author(s)
      Michiko Sasaki
    • Organizer
      42nd National Organic Chemistry Symposium
    • Place of Presentation
      Princeton, NJ, USA
    • Year and Date
      2011-06-05
    • Related Report
      2011 Annual Research Report
  • [Presentation] Enantioselective Generation of Mesomerically-Stabilized Lithiocarbanions and Evaluation of Their Confiaurational Stability2011

    • Author(s)
      Michiko Sasaki
    • Organizer
      42nd National Organic Chemistry Symposium
    • Place of Presentation
      Princeton, NJ, USA
    • Year and Date
      2011-06-05
    • Related Report
      2011 Annual Research Report
  • [Presentation] 共役性電子求引基に隣接するキラルカルバニオンの立体化学的安定性の評価法の開発とその求電子剤による捕捉2011

    • Author(s)
      佐々木道子
    • Organizer
      第9回次世代を担う有機化学シンポジウム
    • Place of Presentation
      東京
    • Year and Date
      2011-05-28
    • Related Report
      2011 Annual Research Report
  • [Presentation] 共役性電子求引性基に隣接するキラルカルバニオンの立体化学的安定性の評価2011

    • Author(s)
      佐々木道子
    • Organizer
      日本薬学会第131年会
    • Place of Presentation
      静岡市
    • Year and Date
      2011-03-31
    • Related Report
      2010 Annual Research Report
  • [Presentation] 光学活性シロキシアレンの合成と[4+2]型環化反応への展開2011

    • Author(s)
      佐々木道子
    • Organizer
      日本薬学会第131年会
    • Place of Presentation
      静岡市
    • Year and Date
      2011-03-31
    • Related Report
      2010 Annual Research Report
  • [Presentation] キラルカルバニオンの立体特異的な求電子反応を利用するL-アミノ酸誘導体の不斉アルキル化2011

    • Author(s)
      佐々木道子
    • Organizer
      日本薬学会第131年会
    • Place of Presentation
      静岡市
    • Year and Date
      2011-03-31
    • Related Report
      2010 Annual Research Report
  • [Presentation] Enantioselective Synthesis of Allenes via Tandem Enantioselective Reduction/Brook Rearrangement2011

    • Author(s)
      Michiko Sasaki
    • Organizer
      10th International Symposium on Organic Reactions
    • Place of Presentation
      Yokohama
    • Related Report
      2012 Final Research Report
  • [Presentation] Chiral Organolithiums Next to a Conjugative Electron-Withdrawing Group: Their Configurational Stability and Enantioselective Trapping by an Electrophile2011

    • Author(s)
      Michiko Sasaki
    • Organizer
      The 242nd National Meeting of the American Chemical Society
    • Place of Presentation
      Denver, Colorado, USA
    • Related Report
      2012 Final Research Report
  • [Presentation] Enantioselective Synthesis of Siloxyallenes from Alkynoylsilanes Via Tandem Enantioselective Reduction/Brook Rearrangement and Their Subsequent Trapping by [4 + 2] Cycloaddition2011

    • Author(s)
      Michiko Sasaki
    • Organizer
      42nd National Organic Chemistry Symposium
    • Place of Presentation
      Princeton, NJ, USA
    • Related Report
      2012 Final Research Report
  • [Presentation] Enantioselective Generation of Mesomerically-Stabilized Lithiocarbanions and Evaluation of Their Configurational Stability2011

    • Author(s)
      Michiko Sasaki
    • Organizer
      42nd National Organic Chemistry Symposium, Princeton University
    • Place of Presentation
      Princeton, NJ, USA
    • Related Report
      2012 Final Research Report
  • [Presentation] 共役性電子求引基に隣接するキラルカルバニオンの立体化学的安定性の評価法の開発2010

    • Author(s)
      佐々木道子
    • Organizer
      第49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
      米子,鳥取
    • Year and Date
      2010-11-06
    • Related Report
      2010 Annual Research Report
  • [Presentation] キラルα-ニトリルカルバニオンの発生と求電子剤による捕捉2010

    • Author(s)
      佐々木道子
    • Organizer
      第49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
      米子,鳥取
    • Year and Date
      2010-11-06
    • Related Report
      2010 Annual Research Report
  • [Presentation] シロキシアレンのエナンチオ選択的合成とその合成反応への展開2010

    • Author(s)
      佐々木道子
    • Organizer
      第49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
      米子,鳥取
    • Year and Date
      2010-11-06
    • Related Report
      2010 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2010

    • Author(s)
      佐々木道子
    • Organizer
      第36回反応と合成の進歩シンポジウム
    • Place of Presentation
      名古屋,愛知
    • Year and Date
      2010-11-02
    • Related Report
      2010 Annual Research Report
  • [Presentation] キラルカルバニオンの立体化学的安定性と求電子剤との反応における立体化学2010

    • Author(s)
      佐々木道子
    • Organizer
      第36回反応と合成の進歩シンポジウム
    • Place of Presentation
      名古屋,愛知
    • Year and Date
      2010-11-01
    • Related Report
      2010 Annual Research Report
  • [Presentation] Enantioselective Synthesis of Siloxyallenes from Alkynylacylsilanes via Tandem Enantioselective Reduction/Brook rearrangement2010

    • Author(s)
      佐々木道子
    • Organizer
      22nd International Symposium on Chirality
    • Place of Presentation
      札幌,北海道
    • Year and Date
      2010-07-14
    • Related Report
      2010 Annual Research Report
  • [Presentation] Solvent Effects on the Configurational Stability of Chiral Carbanions2010

    • Author(s)
      佐々木道子
    • Organizer
      22nd International Symposium on Chirality
    • Place of Presentation
      札幌,北海道
    • Year and Date
      2010-07-14
    • Related Report
      2010 Annual Research Report
  • [Presentation] Enantioselective Synthesis of Siloxyallenes from Alkynylacylsilanes via Tandem Enantioselective Reduction/Brook rearrangement2010

    • Author(s)
      Michiko Sasaki
    • Organizer
      22nd International Symposium on Chirality (Chirality 2010; ISCD-22)
    • Place of Presentation
      Sapporo
    • Related Report
      2012 Final Research Report
  • [Presentation] Solvent Effects on the Configurational Stability of Chiral Carbanions2010

    • Author(s)
      Michiko Sasaki
    • Organizer
      22nd International Symposium on Chirality (Chirality 2010; ISCD-22)
    • Place of Presentation
      Sapporo
    • Related Report
      2012 Final Research Report
  • [Remarks] ホームページ

    • URL

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

    • Related Report
      2012 Final Research Report
  • [Remarks]

    • URL

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

    • Related Report
      2012 Final Research Report
  • [Remarks]

    • URL

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

    • Related Report
      2011 Annual Research Report
  • [Remarks]

    • URL

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

    • Related Report
      2011 Annual Research Report
  • [Remarks]

    • URL

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

    • Related Report
      2010 Annual Research Report
  • [Remarks]

    • URL

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

    • Related Report
      2010 Annual Research Report

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Published: 2010-08-23   Modified: 2019-07-29  

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