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有機分子触媒による分子認識の基盤開拓と反応開発

Publicly Offered Research

Project AreaAdvanced Molecular Transformations by Organocatalysts
Project/Area Number 26105732
Research Category

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

Allocation TypeSingle-year Grants
Review Section Science and Engineering
Research InstitutionKyoto University

Principal Investigator

山田 健一  京都大学, 薬学研究科(研究院), 准教授 (00335184)

Project Period (FY) 2014-04-01 – 2016-03-31
Project Status Completed (Fiscal Year 2015)
Budget Amount *help
¥6,240,000 (Direct Cost: ¥4,800,000、Indirect Cost: ¥1,440,000)
Fiscal Year 2015: ¥3,120,000 (Direct Cost: ¥2,400,000、Indirect Cost: ¥720,000)
Fiscal Year 2014: ¥3,120,000 (Direct Cost: ¥2,400,000、Indirect Cost: ¥720,000)
Keywords含窒素複素環カルベン / 有機分子酸塩基触媒
Outline of Annual Research Achievements

多機能NHC有機触媒の創製、新規有機分子酸塩基触媒の創製、それらを用いる新規不斉反応の開拓を目的として研究を行い、本年度は以下の成果を得た。
(1)昨年度に開発したキラルリン酸触媒による脱離基の活性化手法を応用して不斉SN2反応の開発を検討した。その結果、アミノアルコール類のp-メトキシベンジル化反応による速度論的光学分割を高いエナンチオ選択性で進行させることに成功した。また、NMRによる反応機構解析を行い、上記反応がリン酸エステルを経由する求核触媒反応であることを明らかにした。
(2)昨年度に開発した分子内ベンゾイン型環化反応を用いるイノシトール合成法を非対称ジアルドースへ適用拡大を試みた。その結果、用いるキラルNHC触媒の立体化学と3,4-位の保護基とが反応の位置選択性の制御に重要であることを明らかにするとともに、イノソースの作り分けに成功した。
(3)昨年度開発したNHC触媒によるアルコールの分子内プロパルギルスルホンへの環化反応をアミド類の環化反応へと適用範囲を拡大することに成功した。
(4)昨年度合成に成功した新規グアニジン触媒をもちいると活性メチレン化合物の不斉共役付加反応が高い不斉収率で進行することを見出し、有効な不斉場が構築されていることを確認した。

Research Progress Status

27年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

27年度が最終年度であるため、記入しない。

Report

(2 results)
  • 2015 Annual Research Report
  • 2014 Annual Research Report
  • Research Products

    (49 results)

All 2016 2015 2014

All Journal Article (14 results) (of which Peer Reviewed: 14 results,  Acknowledgement Compliant: 6 results) Presentation (35 results) (of which Int'l Joint Research: 8 results,  Invited: 5 results)

  • [Journal Article] Oxa- and Azacycle-formation via Migrative Cyclization of Sulfonylalkynol and Sulfonylalkynamide with N-Heterocyclic Carbene.2016

    • Author(s)
      K. Yamada
    • Journal Title

      J. Org. Chem

      Volume: 81 Issue: 6 Pages: 2652-2664

    • DOI

      10.1021/acs.joc.6b00182

    • NAID

      120006881403

    • Related Report
      2015 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Striking Difference between Succinimidomethyl and Phthalimidomethyl Radicals in Conjugate Addition to Alkylidenemalonate Initiated by Dimethylzinc.2016

    • Author(s)
      K. Yamada
    • Journal Title

      J. Org. Chem.

      Volume: なし

    • NAID

      120006881404

    • Related Report
      2015 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Organocatalytic Activation of the Leaving Group in the Intramolecular Asymmetric SN2' Reaction.2015

    • Author(s)
      K. Yamada
    • Journal Title

      Angew. Chem. Int. Ed.

      Volume: 54 Issue: 28 Pages: 8263-8266

    • DOI

      10.1002/anie.201502831

    • NAID

      120005670851

    • Related Report
      2015 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Asymmetric Total Synthesis of Tylophorine via a Formal [2+2] Cycloaddition Followed by Migrative Ring Opening of a Cyclobutane.2015

    • Author(s)
      K. Yamada
    • Journal Title

      Synthesis

      Volume: 47 Issue: 18 Pages: 2819-2825

    • DOI

      10.1055/s-0034-1380430

    • Related Report
      2015 Annual Research Report
    • Peer Reviewed
  • [Journal Article] An Arylative Ring Expansion Cascade of Fused Cyclobutenes via Short-Lived Intermediates with Planar Chirality.2015

    • Author(s)
      K. Yamada
    • Journal Title

      J. Am. Chem. Soc.

      Volume: 137 Issue: 30 Pages: 9579-9582

    • DOI

      10.1021/jacs.5b06576

    • Related Report
      2015 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Exploration of Dimethylzinc-Mediated Radical Reactions.2015

    • Author(s)
      K. Yamada
    • Journal Title

      Chem. Rec.

      Volume: 15 Issue: 5 Pages: 854-871

    • DOI

      10.1002/tcr.201500017

    • NAID

      120005689178

    • Related Report
      2015 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Cyclic Model for the Asymmetric Conjugate Addition of Organolithium with Enoate.2015

    • Author(s)
      K. Yamada
    • Journal Title

      Synthesis

      Volume: なし

    • NAID

      120005674638

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed
  • [Journal Article] A Short Synthesis of (+)-β-Lycorane by Asymmetric Conjugate Addition Cascade.2015

    • Author(s)
      Kiyoshi Tomioka
    • Journal Title

      Tetrahedron

      Volume: 71 Issue: 39 Pages: 7222-7226

    • DOI

      10.1016/j.tet.2015.03.014

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Hydrostannylation-Cross-Coupling Strategy for Stereoselective Synthesis of Alkylidenemalonates and Related α,β-Unsaturated Esters2015

    • Author(s)
      Fujiwara, S.; Cadou, R.; Yamaoka, Y.; Takasu, K.; Yamada, K.
    • Journal Title

      Eur. J. Org. Chem.

      Volume: none Issue: 2 Pages: 1264-1272

    • DOI

      10.1021/jo502467m

    • NAID

      120005623273

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Hydrostannylation-Cross-Coupling Strategy for Stereoselective Synthesis of Alkylidenemalonates and Related α,β-Unsaturated Esters.2015

    • Author(s)
      K. Yamada
    • Journal Title

      Eur. J. Org. Chem.

      Volume: なし Issue: 6 Pages: 1264-1272

    • DOI

      10.1002/ejoc.201403429

    • NAID

      120005623273

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis of Steroidal Derivatives Bearing a Small Ring Using a Catalytic [2+2] Cycloaddition and a Ring-Contraction Rearrangement2015

    • Author(s)
      Norihito Arichi, Kenji Hata, Yoshiji Takemoto, Ken-ichi Yamada, Yousuke Yamaoka, Kiyosei Takasu
    • Journal Title

      Tetrahedron

      Volume: 71 Issue: 2 Pages: 233244-233244

    • DOI

      10.1016/j.tet.2014.11.065

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Contiguous radical pivaloyloxymethylation-directed C(sp3)-H iodination of N-tosyl cycloalkanecarbaldimine.2015

    • Author(s)
      Kiyoshi Tomioka
    • Journal Title

      Tetrahedron Letters

      Volume: 56 Issue: 23 Pages: 3086-3089

    • DOI

      10.1016/j.tetlet.2014.11.105

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] N-Heterocyclic Carbene-Catalyzed Benzoin Strategy for Divergent Synthesis of Cyclitol Derivatives from Alditols.2015

    • Author(s)
      K. Yamada
    • Journal Title

      Adv. Synth. Catal.

      Volume: 357 Issue: 1 Pages: 131-147

    • DOI

      10.1002/adsc.201400712

    • NAID

      120005657896

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Radical Aminomethylation of Imines.2014

    • Author(s)
      K. Yamada
    • Journal Title

      J. Org. Chem.

      Volume: 79 Issue: 17 Pages: 8128-8133

    • DOI

      10.1021/jo501332j

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed
  • [Presentation] キラルブレンステッド酸触媒による非対称化を利用したカタランチンの不斉全合成研究2016

    • Author(s)
      山田健一
    • Organizer
      「有機分子触媒による未来型分子変換」第6回公開シンポジウム
    • Place of Presentation
      大阪
    • Year and Date
      2016-01-22
    • Related Report
      2015 Annual Research Report
  • [Presentation] Activation of the leaving group in the chiral phosphoric acid-catalyzed intramolecular asymmetric SN2’ reaction2015

    • Author(s)
      K. Yamada
    • Organizer
      The 2015 International Chemical Congress of Pacific Basin Societies
    • Place of Presentation
      米国
    • Year and Date
      2015-12-15
    • Related Report
      2015 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Migrative Cyclization of Alkynylsulfones Using N-Heterocyclic Carbenes2015

    • Author(s)
      K. Yamada
    • Organizer
      The 2015 International Chemical Congress of Pacific Basin Societies
    • Place of Presentation
      米国
    • Year and Date
      2015-12-15
    • Related Report
      2015 Annual Research Report
    • Int'l Joint Research
  • [Presentation] E/Z-selective synthesis of unsymmetric alkylidenemalonates and its applications2015

    • Author(s)
      K. Yamada
    • Organizer
      The 9th SKO Symposium
    • Place of Presentation
      韓国
    • Year and Date
      2015-11-17
    • Related Report
      2015 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Organocatalytic Activation of the Leaving Group in the Asymmetric Substitution Reaction2015

    • Author(s)
      K. Yamada
    • Organizer
      The 13th International Kyoto Conference on New Aspects of Organic Chemistry (IKCOC-13)
    • Place of Presentation
      京都
    • Year and Date
      2015-11-09
    • Related Report
      2015 Annual Research Report
    • Int'l Joint Research
  • [Presentation] パエスレリンAの全合成2015

    • Author(s)
      山田健一
    • Organizer
      第41回反応と合成の進歩シンポジウム
    • Place of Presentation
      大阪
    • Year and Date
      2015-10-26
    • Related Report
      2015 Annual Research Report
  • [Presentation] 分子内水素結合を介した配座制御による酸化還元応答型色素分子の開発2015

    • Author(s)
      山田健一
    • Organizer
      第26回基礎有機化学討論会
    • Place of Presentation
      愛媛
    • Year and Date
      2015-09-24
    • Related Report
      2015 Annual Research Report
  • [Presentation] シクロブタノールの環縮小転位を利用したpH 応答性蛍光化合物の合成2015

    • Author(s)
      山田健一
    • Organizer
      第26回基礎有機化学討論会
    • Place of Presentation
      愛媛
    • Year and Date
      2015-09-24
    • Related Report
      2015 Annual Research Report
  • [Presentation] ジアルドースのベンゾイン型環化反応を用いるシクリトール類の合成研究2015

    • Author(s)
      山田健一
    • Organizer
      第57回天然有機化合物討論会
    • Place of Presentation
      横浜
    • Year and Date
      2015-09-09
    • Related Report
      2015 Annual Research Report
  • [Presentation] Total Synthesis and Structural Revision of Paesslerin A2015

    • Author(s)
      K. Yamada
    • Organizer
      Inaugural Symposium of the Phytochemical Society of Asia 2015
    • Place of Presentation
      徳島
    • Year and Date
      2015-08-30
    • Related Report
      2015 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Efficient Synthesis of Nitrogen-containing Medium Rings with Ynamides2015

    • Author(s)
      K. Yamada
    • Organizer
      The 25th ISHC Congress
    • Place of Presentation
      米国
    • Year and Date
      2015-08-23
    • Related Report
      2015 Annual Research Report
    • Int'l Joint Research
  • [Presentation] 分子内水素結合による配座制御を利用した酸化還元応答型色素の開発2015

    • Author(s)
      山田健一
    • Organizer
      第35回有機合成若手セミナー
    • Place of Presentation
      京都
    • Year and Date
      2015-08-01
    • Related Report
      2015 Annual Research Report
  • [Presentation] ブレンステッド酸を用いたエン-イナミドの環化反応と天然物合成への応用2015

    • Author(s)
      山田健一
    • Organizer
      第35回有機合成若手セミナー
    • Place of Presentation
      京都
    • Year and Date
      2015-08-01
    • Related Report
      2015 Annual Research Report
  • [Presentation] Total Synthesis of Paesslerin A2015

    • Author(s)
      山田健一
    • Organizer
      The 39th Naito Conference
    • Place of Presentation
      北海道
    • Year and Date
      2015-07-06
    • Related Report
      2015 Annual Research Report
    • Int'l Joint Research
  • [Presentation] The asymmetric intramolecular SN2' reaction catalyzed by chiral phosphoric acid2015

    • Author(s)
      山田健一
    • Organizer
      The 39th Naito Conference
    • Place of Presentation
      北海道
    • Year and Date
      2015-07-06
    • Related Report
      2015 Annual Research Report
    • Int'l Joint Research
  • [Presentation] 面性不斉短寿命中間体を経由する縮環シクロブテンの環拡大反応2015

    • Author(s)
      山田健一
    • Organizer
      Symposium on Molecular Chirality 2015
    • Place of Presentation
      東京
    • Year and Date
      2015-06-12
    • Related Report
      2015 Annual Research Report
  • [Presentation] 求電子種の活性化に基づく触媒的不斉置換反応の開発2015

    • Author(s)
      山田健一
    • Organizer
      第13回次世代を担う有機化学シンポジウム
    • Place of Presentation
      滋賀
    • Year and Date
      2015-05-22
    • Related Report
      2015 Annual Research Report
  • [Presentation] 脱離基の活性化に基づく触媒的分子内不斉SN2'反応の開発2015

    • Author(s)
      山田健一
    • Organizer
      第8回有機触媒シンポジウム
    • Place of Presentation
      沖縄
    • Year and Date
      2015-05-10
    • Related Report
      2015 Annual Research Report
  • [Presentation] N-HETEROCYCLIC CARBENE–CATALYZED BENZOIN STRATEGY FOR DIVERGENT SYNTHESIS OF INOSITOL DERIVATIVES FROM ALDITOLS2014

    • Author(s)
      K. Yamada
    • Organizer
      8th Singapore International Chemistry Conference (SICC-8)
    • Place of Presentation
      シンガポール
    • Year and Date
      2014-12-16
    • Related Report
      2014 Annual Research Report
  • [Presentation] TOTAL SYNTHESIS OF PAESSLERIN A2014

    • Author(s)
      K. Yamada
    • Organizer
      8th Singapore International Chemistry Conference (SICC-8)
    • Place of Presentation
      シンガポール
    • Year and Date
      2014-12-16
    • Related Report
      2014 Annual Research Report
  • [Presentation] Desymmetrization of σ-symmetric acid anhydride by a chiral phosphoric acid2014

    • Author(s)
      K. Yamada
    • Organizer
      The Ninth International Symposium on Integrated Synthesis(ISIS-9)
    • Place of Presentation
      兵庫
    • Year and Date
      2014-11-15
    • Related Report
      2014 Annual Research Report
  • [Presentation] Efficient Synthesis of Medium Ring with Ynamides2014

    • Author(s)
      K. Yamada
    • Organizer
      The Ninth International Symposium on Integrated Synthesis(ISIS-9)
    • Place of Presentation
      兵庫
    • Year and Date
      2014-11-15
    • Related Report
      2014 Annual Research Report
  • [Presentation] 脱離基の活性化に基づく触媒的分子内不斉S N2'反応の開発2014

    • Author(s)
      山田健一
    • Organizer
      第40回反応と合成の進歩シンポジウム
    • Place of Presentation
      仙台
    • Year and Date
      2014-11-10
    • Related Report
      2014 Annual Research Report
  • [Presentation] Palladium-Catalyzed Arylating Ring Expansion of Fused-Cyclobutenes2014

    • Author(s)
      K. Yamada
    • Organizer
      Conference on C-C Bond Cleavage (CCCC)
    • Place of Presentation
      京都
    • Year and Date
      2014-10-25
    • Related Report
      2014 Annual Research Report
  • [Presentation] 多成分連続反応を利用する抗腫瘍活性テルペンPaesslerin Aの全合成2014

    • Author(s)
      山田健一
    • Organizer
      第56回天然有機化合物討論会
    • Place of Presentation
      高知
    • Year and Date
      2014-10-16
    • Related Report
      2014 Annual Research Report
  • [Presentation] 含窒素複素環カルベンを用いる合成反応の開発2014

    • Author(s)
      山田健一
    • Organizer
      第6回化学系若手研究者講演会
    • Place of Presentation
      千葉大学薬学部
    • Year and Date
      2014-09-26
    • Related Report
      2014 Annual Research Report
    • Invited
  • [Presentation] Development of synthetic methodologies utilizing N-heterocyclic carbenes2014

    • Author(s)
      K. Yamada
    • Organizer
      Tampere University of Technology, Department of Chemistry and Bioengineering講演
    • Place of Presentation
      フィンランド
    • Year and Date
      2014-09-22
    • Related Report
      2014 Annual Research Report
    • Invited
  • [Presentation] ENHANCED RATE AND SELECTIVITY BY CARBOXYLATE SALT AS A BASIC COCATALYST IN CHIRAL NHC-CATALYZED ASYMMETRIC ACYLATION OF SECONDARY ALCOHOLS2014

    • Author(s)
      K. Yamada
    • Organizer
      Molecular Complexity in Modern Chemistry (MCMC-2014)
    • Place of Presentation
      ロシア
    • Year and Date
      2014-09-17
    • Related Report
      2014 Annual Research Report
  • [Presentation] 縮環シクロブタノールの環縮小転位を利用したtylophorine類の合成2014

    • Author(s)
      山田健一
    • Organizer
      第44回複素環化学討論会
    • Place of Presentation
      北海道
    • Year and Date
      2014-09-10
    • Related Report
      2014 Annual Research Report
  • [Presentation] 縮環シクロブタノールを経る多環芳香族化合物の合成と反応機構2014

    • Author(s)
      山田健一
    • Organizer
      第25回基礎有機化学討論会
    • Place of Presentation
      仙台
    • Year and Date
      2014-09-07
    • Related Report
      2014 Annual Research Report
  • [Presentation] "アルキリデンマロネートおよび類縁体の E / Z 選択的な合成法の開発 "2014

    • Author(s)
      山田健一
    • Organizer
      日本プロセス化学会2014サマーシンポジウム
    • Place of Presentation
      東京
    • Year and Date
      2014-08-01
    • Related Report
      2014 Annual Research Report
  • [Presentation] Synthesis of 2,3,4,5-tetra-substituted pyrroles via a base-promoted double Michael reaction of oxime-enoates2014

    • Author(s)
      K. Yamada
    • Organizer
      20th International Conference on Organic Synthesis
    • Place of Presentation
      ハンガリー
    • Year and Date
      2014-07-01 – 2014-07-02
    • Related Report
      2014 Annual Research Report
  • [Presentation] Synthesis of Steroid Derivatives Bearing a Small Ring for the Conformational Fixation of D-Ring Side Chain2014

    • Author(s)
      K. Yamada
    • Organizer
      20th International Conference on Organic Synthesis
    • Place of Presentation
      ハンガリー
    • Year and Date
      2014-07-01 – 2014-07-02
    • Related Report
      2014 Annual Research Report
  • [Presentation] NHC触媒による触媒によるa4極性転換反応の開発2014

    • Author(s)
      山田健一
    • Organizer
      新学術領域研究 分子活性化―有機分子触媒 合同シンポジウム
    • Place of Presentation
      北海道
    • Year and Date
      2014-06-21
    • Related Report
      2014 Annual Research Report
    • Invited
  • [Presentation] 効率的縮環シクロブタノール合成と多環芳香族炭化水素への応用2014

    • Author(s)
      山田健一
    • Organizer
      第12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
      2014-05-23
    • Related Report
      2014 Annual Research Report

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Published: 2014-04-04   Modified: 2018-03-28  

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