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Development of new synthetic methods based on catalytic skeletal rearrangement reactions

Research Project

Project/Area Number 20H02731
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Review Section Basic Section 33020:Synthetic organic chemistry-related
Research InstitutionTohoku University

Principal Investigator

Nakamura Itaru  東北大学, 理学研究科, 准教授 (00333899)

Project Period (FY) 2020-04-01 – 2023-03-31
Project Status Completed (Fiscal Year 2022)
Budget Amount *help
¥17,810,000 (Direct Cost: ¥13,700,000、Indirect Cost: ¥4,110,000)
Fiscal Year 2022: ¥5,590,000 (Direct Cost: ¥4,300,000、Indirect Cost: ¥1,290,000)
Fiscal Year 2021: ¥5,590,000 (Direct Cost: ¥4,300,000、Indirect Cost: ¥1,290,000)
Fiscal Year 2020: ¥6,630,000 (Direct Cost: ¥5,100,000、Indirect Cost: ¥1,530,000)
Keywords転位 / 銅触媒 / 金触媒 / 酸化的付加 / アニリン / ヘテロ環 / 挿入反応 / 多置換アルケン / 効率合成 / 転位反応 / Diels-Alder反応 / 金属触媒
Outline of Research at the Start

触媒的骨格転位により分子の自在合成を実現するための諸問題の解決を目指す。特に「立体的に混雑した位置での結合構築」「多様な置換基の位置選択的導入」「リン官能基と共存する触媒反応設計」に焦点を当てた新手法を開発し、有機合成の発展に寄与する。本プロジェクトの遂行により「多官能基化多環式芳香族化合物」「軸不斉」「高官能基化リン化合物」の効率合成が可能となり材料開発および医薬品開発への波及効果をもたらす。活性化の鍵となる「カチオン性NHC金属触媒と転位アルコキシ基の間に働く分散相互作用による遷移状態の安定化」の学術的理解を深め、ルイス酸の化学に進展をもたらす。

Outline of Final Research Achievements

We have established an efficient method for the synthesis of various polysubstituted aniline compounds and three-dimensional molecules based on the cationic copper-catalyzed [1,3]-oxygen rearrangement reaction. The oxygen rearrangement reaction proceeds ortho-selectively on naphthalene and indole moieties, and can be regarded as complementary to peri-selective C-H oxidation reactions. We have developed catalytic [1,3]-nitrogen rearrangement reaction, which is a complementary to [1,3]-oxygen rearrangement as a synthetic method for ortho-aminophenol derivatives. In the skeletal rearrangement reaction initiated by catalytic π-activation of alkynes, we developed the construction of distorted three-membered heterocycles by consecutive N-S/O-S bond cleavage reactions of N-sulfinylimines. Furthermore, we developed a gold-catalyzed reaction in which a sulfenamide N-S bond is inserted into a terminal alkyne.

Academic Significance and Societal Importance of the Research Achievements

カチオン性銅触媒に対するN-O結合の酸化的付加に関して、窒素および酸素原子上の電子密度の増加により加速される新たな形式を明らかにしたことは学術的な進歩といえる。この素反応を利用した反応設計により、多様な官能基が置換された窒素および酸素が含まれる有機化合物の効率合成へと展開されることが期待できる。スルフィニルイミンの金触媒による骨格転位反応は新規含窒素および含硫黄ヘテロ環の網羅的構築を可能とする方法論を創出し複素環化学の進展に寄与した。多置換ヘテロ環化合物および多置換芳香族化合物は医薬品・材料分子などの重要骨格であり新たな機能創成を可能とする合成化学の社会的意義に貢献したものと考えられる。

Report

(4 results)
  • 2022 Annual Research Report   Final Research Report ( PDF )
  • 2021 Annual Research Report
  • 2020 Annual Research Report
  • Research Products

    (19 results)

All 2022 2021 2020 Other

All Journal Article (7 results) (of which Peer Reviewed: 6 results) Presentation (10 results) (of which Int'l Joint Research: 2 results,  Invited: 8 results) Remarks (2 results)

  • [Journal Article] Gold-Catalyzed Intermolecular Alkyne Insertion into the N?S Bond in Sulfenamides2022

    • Author(s)
      Asoh Takato、Tashiro Hiroki、Terada Masahiro、Nakamura Itaru
    • Journal Title

      Organic Letters

      Volume: 24 Issue: 50 Pages: 9264-9268

    • DOI

      10.1021/acs.orglett.2c03831

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Consecutive O-S/N-S Bond Cleavage in Gold‐Catalyzed Rearrangement Reactions of Alkynyl N‐Sulfinylimines2021

    • Author(s)
      Tashiro Hiroki、Terada Masahiro、Nakamura Itaru
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 60 Issue: 22 Pages: 12248-12252

    • DOI

      10.1002/anie.202100207

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Cu-Catalyzed [1,3]-Alkoxy Rearrangement/Diels?Alder Cascade Reactions via in Situ Generation of Functionalized ortho-Quinol Imines2021

    • Author(s)
      Nakamura Itaru、Masukawa Kazuki、Ishida Yasuhiro、Terada Masahiro
    • Journal Title

      Organic Letters

      Volume: 23 Issue: 11 Pages: 4127-4132

    • DOI

      10.1021/acs.orglett.1c00995

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Copper-catalyzed [1,3]-alkoxy rearrangement for the selective synthesis of polycyclic ortho-aminoarenol derivatives2021

    • Author(s)
      Nakamura Itaru、Nozawa Satoru、Ishida Yasuhiro、Muranushi Ichiro、Mayerweg Alexandra、Terada Masahiro
    • Journal Title

      Organic Chemistry Frontiers

      Volume: 8 Issue: 22 Pages: 6390-6394

    • DOI

      10.1039/d1qo01189h

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis of meta-Substituted Anilines via Copper-Catalyzed [1,3]-Methoxy Rearrangement2020

    • Author(s)
      Nakamura Itaru、Tashiro Hiroki、Ishida Yasuhiro、Terada Masahiro
    • Journal Title

      Organic Letters

      Volume: 22 Issue: 10 Pages: 3794-3798

    • DOI

      10.1021/acs.orglett.0c01009

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Exo‐Cyclization: Intermolecular Methylene Transfer Sequence in Au‐Catalyzed Reactions of O‐Homopropargylic Oximes2020

    • Author(s)
      Nakamura Itaru、Hirayama Arinobu、Gima Shinya、Terada Masahiro
    • Journal Title

      Chemistry A European Journal

      Volume: 26 Issue: 68 Pages: 15816-15820

    • DOI

      10.1002/chem.202002764

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Efficient Synthesis of O-tert-Propargylic Oximes via Nicholas Reaction2020

    • Author(s)
      Nakamura Itaru、Shiga Keigo、Suzuki Mao、Terada Masahiro
    • Journal Title

      Synthesis

      Volume: 52 Issue: 22 Pages: 3461-3465

    • DOI

      10.1055/s-0040-1707191

    • Related Report
      2020 Annual Research Report
  • [Presentation] 第11族金属錯体触媒による転位反応の新展開2022

    • Author(s)
      中村達
    • Organizer
      第130回触媒討論会 有機金属・分子触媒セッション
    • Related Report
      2022 Annual Research Report
    • Invited
  • [Presentation] 触媒的骨格転位を基盤とする新合成手法の開発2022

    • Author(s)
      中村達
    • Organizer
      有機合成化学協会 企業冠賞受賞講演会
    • Related Report
      2022 Annual Research Report
    • Invited
  • [Presentation] 触媒的骨格転位を鍵とする新しい合成手法の開拓2022

    • Author(s)
      中村 達
    • Organizer
      豊橋技術科学大学講演会
    • Related Report
      2021 Annual Research Report
    • Invited
  • [Presentation] 触媒的骨格転位を鍵とする新しい合成手法の開拓2021

    • Author(s)
      中村 達
    • Organizer
      大阪市立大学教育推進本部経費事業グローバル人材育成談話会セミナー
    • Related Report
      2021 Annual Research Report
    • Invited
  • [Presentation] Consecutive O-S/N-S bond cleavage in Au-catalyzed rearrangement reactions of alkynyl N-sulfinylimines2021

    • Author(s)
      H. Tashiro, M. Terada, I. Nakamura
    • Organizer
      Sulfur Rush: Organosulfur Frontiers (#364) in Pacifichem 2021
    • Related Report
      2021 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Synthesis of multi-substituted anilines via Cu-catalyzed [1,3]-alkoxy rearrangement2021

    • Author(s)
      I. Nakamura, Y. Ishida, H. Tashiro, T. Jo, M. Terada
    • Organizer
      Base Metal-Catalyzed Reactions (#384) in Pacifichem 2021
    • Related Report
      2021 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Recent Progress on Catalytic Skeletal Rearrangement Reactions for Heterocyclic Synthesis2021

    • Author(s)
      Itaru Nakamura
    • Organizer
      令和3年度化学系学協会東北大会有機化学コロキウム
    • Related Report
      2021 Annual Research Report
    • Invited
  • [Presentation] 触媒的骨格転位を鍵とする新しい合成手法の開拓2021

    • Author(s)
      中村達
    • Organizer
      近畿化学協会ヘテロ原子部会2020年度第3回懇話会
    • Related Report
      2020 Annual Research Report
    • Invited
  • [Presentation] 触媒的骨格転位を鍵とする新しい合成手法の開拓2020

    • Author(s)
      中村達
    • Organizer
      九州大学大学院総合理工学府 先端有機化学講義講演会
    • Related Report
      2020 Annual Research Report
    • Invited
  • [Presentation] 触媒的骨格転位を鍵とする新しい合成手法の開拓2020

    • Author(s)
      中村達
    • Organizer
      有機合成化学協会東海支部総合講演会
    • Related Report
      2020 Annual Research Report
    • Invited
  • [Remarks] 東北大学大学院理学研究科化学専攻反応有機化学研究室

    • URL

      http://www.orgreact.sakura.ne.jp/index.html

    • Related Report
      2022 Annual Research Report 2021 Annual Research Report
  • [Remarks] 東北大学大学院理学研究科化学専攻反応有機化学研究室ホームページ

    • URL

      http://www.orgreact.sakura.ne.jp/

    • Related Report
      2020 Annual Research Report

URL: 

Published: 2020-04-28   Modified: 2024-01-30  

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