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Development of novel allylmetal generation method and its application

Research Project

Project/Area Number 25860004
Research Category

Grant-in-Aid for Young Scientists (B)

Allocation TypeMulti-year Fund
Research Field Chemical pharmacy
Research InstitutionThe University of Tokyo

Principal Investigator

SHIMIZU Yohei  東京大学, 薬学研究科(研究院), 助教 (60609816)

Project Period (FY) 2013-04-01 – 2015-03-31
Project Status Completed (Fiscal Year 2014)
Budget Amount *help
¥4,030,000 (Direct Cost: ¥3,100,000、Indirect Cost: ¥930,000)
Fiscal Year 2014: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000)
Fiscal Year 2013: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000)
Keywordsアリル銅 / 不斉触媒 / インドール / アレン / アリル化 / 触媒 / 不斉反応 / 銅 / 不斉
Outline of Final Research Achievements

We developed a novel method to generate allylcopper species from an allenylanilide, which possesses both an allene moiety and an aniline moiety in one molecule. Cu(I) catalyst facilitates a generation of allylcopper species along with formation of indole structure. The generated allylcopper species can work as nucleophile to various carbonyl compounds including ketones.
The reaction proceeded in enantioselective manner by utilizing a chiral diphosphine ligand. Thus the reaction produced chiral 2-(2-hydroxyethyl)indoles efficiently, whose scaffold is difficult to construct by other means.
The developed method is unique in simultaneous construction of indole structure and elongation of carbon scaffold.

Report

(3 results)
  • 2014 Annual Research Report   Final Research Report ( PDF )
  • 2013 Research-status Report
  • Research Products

    (27 results)

All 2015 2014 2013 Other

All Journal Article (4 results) (of which Peer Reviewed: 4 results,  Open Access: 1 results,  Acknowledgement Compliant: 2 results) Presentation (21 results) Remarks (2 results)

  • [Journal Article] Design and synthesis of biotin analogues reversibly binding with streptavidin2015

    • Author(s)
      Tomohiro Yamamoto, Kiyoshi Aoki, Akira Sugiyama, Hirofumi Doi, Tatsuhiko Kodama, Yohei Shimizu, Motomu Kanai
    • Journal Title

      Chemistry - An Asian Journal

      Volume: 10 Issue: 4 Pages: 1071-1078

    • DOI

      10.1002/asia.201500120

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] A Catalytic C-C Bond-Formation with Minimal Use of Protecting Groups: Construction of Functionalized Isotetronic Acid Derivatives2014

    • Author(s)
      Shimizu, Y.; Yasuda, K.; Kanai, M.
    • Journal Title

      Heterocycles

      Volume: 88 Issue: 2 Pages: 919-927

    • DOI

      10.3987/com-13-s(s)81

    • Related Report
      2014 Annual Research Report 2013 Research-status Report
    • Peer Reviewed
  • [Journal Article] Catalytic enantioselective synthesis of 2-(2- hydroxyethyl)indole scaffolds via consecutive intramolecular amido-cupration of allenes and asymmetric addition of carbonyl compounds2014

    • Author(s)
      Prasanna Kumara Chikkade, Yohei Shimizua, Motomu Kanai
    • Journal Title

      Chemical Science

      Volume: 5 Issue: 4 Pages: 1585-1590

    • DOI

      10.1039/c3sc52803k

    • Related Report
      2014 Annual Research Report 2013 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Copper-Catalyzed Regio- and Stereoselective Intermolecular Three- Component Oxyarylation of Allenes2014

    • Author(s)
      Taisuke Itoh, Yohei Shimizu, Motomu Kanai
    • Journal Title

      Organic Letters

      Volume: 16 Issue: 10 Pages: 2736-2739

    • DOI

      10.1021/ol501022d

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Presentation] カルボン酸選択的Mannich型反応の開発2015

    • Author(s)
      山本倫広、森田雄也、清水洋平、金井求
    • Organizer
      日本化学会第95春季年会(2015)
    • Place of Presentation
      日本大学 理工学部船橋キャンパス
    • Year and Date
      2015-03-26 – 2015-03-29
    • Related Report
      2014 Annual Research Report
  • [Presentation] Rapid Sythesis of Sialic Acid Derivatives via Ligand-Controlled, Stereodivergent Propagylation of Unprotected Aldoses2015

    • Author(s)
      魏暁峰、清水洋平、金井求
    • Organizer
      日本化学会第95春季年会(2015)
    • Place of Presentation
      日本大学 理工学部船橋キャンパス
    • Year and Date
      2015-03-26 – 2015-03-29
    • Related Report
      2014 Annual Research Report
  • [Presentation] 無保護糖を基質としたジアステレオ選択的触媒的プロパルギル化反応の開発2015

    • Author(s)
      清水洋平、魏暁峰、金井求
    • Organizer
      日本薬学会第135年会(神戸)
    • Place of Presentation
      神戸学院大学
    • Year and Date
      2015-03-25 – 2015-03-28
    • Related Report
      2014 Annual Research Report
  • [Presentation] カルボン酸選択的な触媒的不斉Mannich型反応の開発2015

    • Author(s)
      森田雄也、山本倫広、清水洋平、金井求
    • Organizer
      日本薬学会第135年会(神戸)
    • Place of Presentation
      神戸学院大学
    • Year and Date
      2015-03-25 – 2015-03-28
    • Related Report
      2014 Annual Research Report
  • [Presentation] 銅触媒を用いたオレフィンのオキシボリル化反応の開発2015

    • Author(s)
      伊藤太亮、清水洋平、金井求
    • Organizer
      日本薬学会第135年会(神戸)
    • Place of Presentation
      神戸学院大学
    • Year and Date
      2015-03-25 – 2015-03-28
    • Related Report
      2014 Annual Research Report
  • [Presentation] 保護基の使用を最小限に抑えたザナミビルの合成研究2015

    • Author(s)
      伊藤創一、木村康明、清水洋平、金井求
    • Organizer
      日本薬学会第135年会(神戸)
    • Place of Presentation
      神戸学院大学
    • Year and Date
      2015-03-25 – 2015-03-28
    • Related Report
      2014 Annual Research Report
  • [Presentation] プレターゲティング治療を目指したビオチン誘導体の合成研究2015

    • Author(s)
      高津まり、清水洋平、杉山暁、土居洋文、児玉龍彦、金井求
    • Organizer
      日本薬学会第135年会(神戸)
    • Place of Presentation
      兵庫医療大学
    • Year and Date
      2015-03-25 – 2015-03-28
    • Related Report
      2014 Annual Research Report
  • [Presentation] 銅触媒を用いたアレンの位置選択的な分子間オキシアリール化反応の開発2014

    • Author(s)
      伊藤太亮、清水洋平、金井求
    • Organizer
      日本プロセス化学会2014サマーシンポジウム
    • Place of Presentation
      タワーホール船堀
    • Year and Date
      2014-07-31 – 2014-08-01
    • Related Report
      2014 Annual Research Report
  • [Presentation] Copper-Catalyzed Regio- and Stereoselective Intermolecular Three-Component Oxyarylation of Allenes2014

    • Author(s)
      Taisuke Itoh, Yohei Shimizu, Motomu Kanai
    • Organizer
      XXVI International Conference on Organometallic Chemistry (ICOMC 2014)
    • Place of Presentation
      Royton Sapporo
    • Year and Date
      2014-07-13 – 2014-07-18
    • Related Report
      2014 Annual Research Report
  • [Presentation] Copper-Catalyzed Regio- and Stereoselective Intermolecular Three-Component Oxyarylation of Allenes2014

    • Author(s)
      Yohei Shimizu,Taisuke Itoh, Motomu Kanai
    • Organizer
      the 19th International Symposium on Homogeneous Catalysis
    • Place of Presentation
      Ottawa Convention Center, Canada
    • Year and Date
      2014-07-06 – 2014-07-11
    • Related Report
      2014 Annual Research Report
  • [Presentation] 銅触媒を用いたアレンの位置選択的な分子間オキシアリール化反応の開発2014

    • Author(s)
      伊藤太亮、清水洋平、金井求
    • Organizer
      第105回有機合成シンポジウム
    • Place of Presentation
      東工大大岡山キャンパス
    • Year and Date
      2014-06-10 – 2014-06-11
    • Related Report
      2014 Annual Research Report
  • [Presentation] 一価銅触媒によるカスケード反応を用いた光学活性インドール誘導体の合成法2014

    • Author(s)
      清水洋平、Prasanna Kumara Chikkade、金井求
    • Organizer
      日本薬学会第134年会(熊本)
    • Place of Presentation
      熊本県、熊本大学
    • Related Report
      2013 Research-status Report
  • [Presentation] 無保護の糖を基質とした触媒的プロパギル化反応の開発2014

    • Author(s)
      魏暁峰、清水洋平、金井求
    • Organizer
      日本薬学会第134年会(熊本)
    • Place of Presentation
      熊本県、熊本大学
    • Related Report
      2013 Research-status Report
  • [Presentation] 保護基フリー合成を目指したカルボン酸直截的アルドール反応及びMannich型反応の開発2014

    • Author(s)
      森田雄也、清水洋平、金井求
    • Organizer
      日本薬学会第134年会(熊本)
    • Place of Presentation
      熊本県、熊本大学
    • Related Report
      2013 Research-status Report
  • [Presentation] 銅触媒を用いた求核的アリル金属種の触媒的発生法の開発2014

    • Author(s)
      伊藤太亮、清水洋平、金井求
    • Organizer
      日本薬学会第134年会(熊本)
    • Place of Presentation
      熊本県、熊本大学
    • Related Report
      2013 Research-status Report
  • [Presentation] プロトン性官能基存在下における一価銅を利用したC-C結合形成反応2013

    • Author(s)
      清水洋平、施世良、Prasanna Kumara Chikkade、魏暁峰、川井準也、金井求
    • Organizer
      第11回次世代を担う有機化学シンポジウム
    • Place of Presentation
      東京都、日本薬学会長井記念ホール
    • Related Report
      2013 Research-status Report
  • [Presentation] Copper-catalyzed carbo-oxydation of allenes2013

    • Author(s)
      伊藤太亮、清水洋平、金井求
    • Organizer
      第48回天然物化学談話会
    • Place of Presentation
      滋賀県大津市 アヤハレークサイドホテル
    • Related Report
      2013 Research-status Report
  • [Presentation] Cu(I)-Catalyzed Diastereoselective C-glycosidation of Unprotected Sugars2013

    • Author(s)
      Xiao-Feng Wei, Shi-Liang Shi, Yohei Shimizu, Motomu Kanai
    • Organizer
      10th International Symposium on Carbanion Chemistry (ISCC-10)
    • Place of Presentation
      京都府、同志社大学、寒梅館
    • Related Report
      2013 Research-status Report
  • [Presentation] In situ Catalytic Generation of Allyl Copper Species and its Direct Use for Asymmetric Allylation2013

    • Author(s)
      Yohei Shimizu, Prasanna Kumara Chikkade, Junya Kawai, Motomu Kanai
    • Organizer
      Frontiers in Chemistry, Armenia
    • Place of Presentation
      Ani Plaza Hotel, Yerevan, Armenia
    • Related Report
      2013 Research-status Report
  • [Presentation] In situ Catalytic Generation of Allyl Copper Species and its Direct Use for Asymmetric Allylation2013

    • Author(s)
      Yohei Shimizu, Prasanna Kumara Chikkade, Junya Kawai, Motomu Kanai
    • Organizer
      The 8th International Conference on Cutting-Edge Organic Chemistry in Asia (ICCEOCA-8) The 4th New Phase International Conference on Cutting-Edge Organic Chemistry in Asia (NICCEOCA-4)
    • Place of Presentation
      大阪府、Grand Cube Osaka
    • Related Report
      2013 Research-status Report
  • [Presentation] 保護基の使用を最小限に抑えたザナミビルの合成研究

    • Author(s)
      伊藤創一、木村康明、清水洋平、金井求
    • Organizer
      日本化学会第94春季年会(2014)
    • Place of Presentation
      愛知県、名古屋大学 東山キャンパス
    • Related Report
      2013 Research-status Report
  • [Remarks] Synthetic Organic Chemistry Lab.

    • URL

      http://www.f.u-tokyo.ac.jp/~kanai/index.html

    • Related Report
      2014 Annual Research Report
  • [Remarks] Synthetic Organic Chemistry Lab.

    • URL

      http://www.f.u-tokyo.ac.jp/~kanai/publication/index.html

    • Related Report
      2013 Research-status Report

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Published: 2014-07-25   Modified: 2019-07-29  

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