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Development of C-H bond-cleaving intramolecular addition reactions toward the facile construction of effective cyclic frameworks

Research Project

Project/Area Number 19K05481
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Review Section Basic Section 33020:Synthetic organic chemistry-related
Research InstitutionNational Institute of Advanced Industrial Science and Technology

Principal Investigator

Minami Yasunori  国立研究開発法人産業技術総合研究所, 材料・化学領域, 主任研究員 (60613362)

Project Period (FY) 2019-04-01 – 2023-03-31
Project Status Completed (Fiscal Year 2022)
Budget Amount *help
¥4,420,000 (Direct Cost: ¥3,400,000、Indirect Cost: ¥1,020,000)
Fiscal Year 2021: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
Fiscal Year 2020: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
Fiscal Year 2019: ¥1,820,000 (Direct Cost: ¥1,400,000、Indirect Cost: ¥420,000)
Keywords不飽和結合化合物 / 付加反応 / 環状化合物 / 有機ケイ素化合物 / 金属触媒 / 炭素-水素結合
Outline of Research at the Start

本研究では,申請者が独自に開発している「パラジウム/有機酸協働触媒によるアルキンの活性化法」を活用して,ビニル炭素-水素結合および脂肪族炭素-水素結合を切断してアルキンに分子内付加させる新規環化反応を開発する.合成中間体としての有用性に加えて薬学的に関心の高い含ケイ素環状化合物を中心に,既存法では直截構築が難しい複素芳香族化合物や脂環式化合物を合成標的とする.

Outline of Final Research Achievements

Based on “the activation of alkynes by a palladium/acid catalyst toward carbon-hydrogen bond cleavages” developed by the applicant, I found catalytic intramolecular hydroalkenylaiton of alkynes via vinlycarbon-hydrogen bond cleavage. This reslut opened the new construction of siloles having various substituents. In addition, this catalytic methodology was applied to the carbon-hydrogen bond cleavage on the simple organocyclic compounds followed by the intermolecular insertion of alkynes that I did not anticipate. Based on these findings, I found a novel construction reaction for organosilicon compounds via the activation of stable aliphatic carbon-hydrogen bonds.

Academic Significance and Societal Importance of the Research Achievements

本研究は,安定な炭素-水素結合を位置選択的に変換する新たな触媒手法を提示するものである.本成果は,将来的に高い需要が見込まれる含ケイ素環状化合物を中心に,薬学的に重要さまざまな環状化合物の直截合成法の確立に向けた礎になると期待している.本研究で開発した反応手法は,量論量の廃棄物を生じないで生成物を与える.すなわち,資源の有効利用を可能にする環境調和に優れた手法として,社会的意義が高いと考えている.

Report

(5 results)
  • 2022 Annual Research Report   Final Research Report ( PDF )
  • 2021 Research-status Report
  • 2020 Research-status Report
  • 2019 Research-status Report
  • Research Products

    (9 results)

All 2023 2022 2021 2020 Other

All Int'l Joint Research (2 results) Journal Article (2 results) (of which Peer Reviewed: 2 results) Presentation (4 results) (of which Int'l Joint Research: 1 results,  Invited: 3 results) Remarks (1 results)

  • [Int'l Joint Research] Universitat de Girona(スペイン)

    • Related Report
      2020 Research-status Report
  • [Int'l Joint Research] Universitat de Girona(スペイン)

    • Related Report
      2019 Research-status Report
  • [Journal Article] Facile Construction of Furanoacenes by a Three‐Step Sequence Going through Disilyl‐ exo ‐cyclic Dienes2020

    • Author(s)
      Minami Yasunori、Furuya Yuki、Hiyama Tamejiro
    • Journal Title

      Chemistry - A European Journal

      Volume: 26 Issue: 43 Pages: 9471-9474

    • DOI

      10.1002/chem.202001119

    • Related Report
      2020 Research-status Report
    • Peer Reviewed
  • [Journal Article] Palladium/Carboxylic Acid‐catalyzed Alkenylation of Furfural and its Derivatives Using Alkynes2020

    • Author(s)
      Minami Yasunori、Miyamoto Hitomi、Nakajima Yumiko
    • Journal Title

      ChemCatChem

      Volume: 13 Issue: 3 Pages: 855-858

    • DOI

      10.1002/cctc.202001685

    • Related Report
      2020 Research-status Report
    • Peer Reviewed
  • [Presentation] 安定プラスチックの化学分解にむけて -スーパーエンプラの解重合-2023

    • Author(s)
      南 安規
    • Organizer
      第4回有機化学講演会
    • Related Report
      2022 Annual Research Report
    • Invited
  • [Presentation] 溶けない,硬いプラスチックを化学分解する - スーパーエンプラの解重合 -2022

    • Author(s)
      南 安規
    • Organizer
      第 4 回 産総研科学研究シンポジウム
    • Related Report
      2022 Annual Research Report
    • Invited
  • [Presentation] Palladium/Carboxylic acid-catalyzed Alkenylation of Arenes via Carbon-Hydrogen Bond Cleavage2021

    • Author(s)
      Yasunori Minami
    • Organizer
      5th International Conference on Catalysis and Chemical Engineering
    • Related Report
      2020 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] パラジウム/カルボン酸触媒を用いるフルフラール類のアルキンによるアルケニル化反応2021

    • Author(s)
      南 安規,宮本仁美,中島裕美子
    • Organizer
      日本化学会 第101回春季年会
    • Related Report
      2020 Research-status Report
  • [Remarks] 産業技術総合研究所 材料化学領域 触媒化学融合研究センター ケイ素化学チーム

    • URL

      http://irc3.aist.go.jp/incorporate/team/organosilicon-chemistry/

    • Related Report
      2022 Annual Research Report 2021 Research-status Report 2020 Research-status Report

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Published: 2019-04-18   Modified: 2024-01-30  

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