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Novel Synthesis of Polycyclic Aromatic Compounds by Polymerization and Chain Scission

Research Project

Project/Area Number 22K19030
Research Category

Grant-in-Aid for Challenging Research (Exploratory)

Allocation TypeMulti-year Fund
Review Section Medium-sized Section 33:Organic chemistry and related fields
Research InstitutionOsaka University

Principal Investigator

Shintani Ryo  大阪大学, 大学院基礎工学研究科, 教授 (50372561)

Project Period (FY) 2022-06-30 – 2024-03-31
Project Status Completed (Fiscal Year 2023)
Budget Amount *help
¥6,500,000 (Direct Cost: ¥5,000,000、Indirect Cost: ¥1,500,000)
Fiscal Year 2023: ¥3,250,000 (Direct Cost: ¥2,500,000、Indirect Cost: ¥750,000)
Fiscal Year 2022: ¥3,250,000 (Direct Cost: ¥2,500,000、Indirect Cost: ¥750,000)
Keywords多環芳香族化合物 / 重合反応 / 縫合重合 / アルケン異性化 / 鎖切断反応
Outline of Research at the Start

拡張π電子系に基づく機能性有機材料の開発において、既知の合成法を駆使しても望みの構造や機能をもつ分子が確実かつ容易に合成できるわけではない。本研究では、入手容易な低分子化合物を一旦重合することで、その方法以外では合成が困難な繰返し構造をもつπ共役ポリマーへと導き、生じた繰返し単位を低分子として切り出すことにより、従来法では実現困難な画期的低分子化合物合成法の開発を目指す。

Outline of Final Research Achievements

Development and utilization of functional organic materials based on extended π-electron systems have been actively explored in recent years, but accessible molecular structures are highly limited. In this research project, we aimed to develop a new process involving the synthesis of polymers possessing polycyclic aromatic units by polymerization of linear molecules followed by cleavage of the chain. As a result, we established a synthetic method of poly(arylenevinylene)s having fused tetracyclic aromatic repeating units by stitching polymerization and subsequent alkene isomerization. In addition, various conditions were investigated for the chain scission of the obtained polymers, and the generation of low molecular weight products were confirmed.

Academic Significance and Societal Importance of the Research Achievements

本研究では、別々の研究分野として捉えられがちな低分子有機化合物の合成と有機高分子合成の垣根を取り除き、従来の合成法ではアクセス困難な低分子化合物の精密合成において、ポリマーを経由する「重合反応+鎖切断」というアプローチを新しい有効な選択肢として示し、方法論として確立することを目標とした。今回の研究期間では一定程度の進捗であったが、その成果は将来的な新しい方法論としての展開につながるものであり、学術的な意義は非常に大きいと考えられる。

Report

(3 results)
  • 2023 Annual Research Report   Final Research Report ( PDF )
  • 2022 Research-status Report
  • Research Products

    (15 results)

All 2024 2023 2022

All Journal Article (3 results) (of which Peer Reviewed: 3 results,  Open Access: 1 results) Presentation (12 results) (of which Int'l Joint Research: 2 results,  Invited: 5 results)

  • [Journal Article] Palladium-catalyzed synthesis of benzosilacyclobutenes via position-selective C(sp3)-H arylation2023

    • Author(s)
      Hamada Naoya、Hayashi Daigo、Shintani Ryo
    • Journal Title

      Chemical Communications

      Volume: 59 Issue: 59 Pages: 9122-9125

    • DOI

      10.1039/d3cc00442b

    • Related Report
      2023 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Palladium‐Catalyzed Skeletal Rearrangement of Substituted 2‐Silylaryl Triflates via 1,5‐C-Pd/C-Si Bond Exchange2023

    • Author(s)
      Hayashi Daigo、Tsuda Tomohiro、Shintani Ryo
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 62 Issue: 50

    • DOI

      10.1002/anie.202313171

    • Related Report
      2023 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis of Poly(arylenevinylene)s by Rhodium-Catalyzed Stitching Polymerization/Alkene Isomerization2022

    • Author(s)
      Togawa, S.; Shintani, R.
    • Journal Title

      J. Am. Chem. Soc.

      Volume: 144 Issue: 40 Pages: 18545-18551

    • DOI

      10.1021/jacs.2c07835

    • Related Report
      2022 Research-status Report
    • Peer Reviewed
  • [Presentation] ラジカル縫合重合の開発による新規架橋型ポリマーの合成2024

    • Author(s)
      浜田祐介、外川蒼野、新谷 亮
    • Organizer
      日本化学会第104春季年会
    • Related Report
      2023 Annual Research Report
  • [Presentation] ロジウム触媒を用いた縫合反応と続く遠隔位での脱水反応による新規縮環オリゴシロールの合成2024

    • Author(s)
      守田壮輝、新谷 亮
    • Organizer
      日本化学会第104春季年会
    • Related Report
      2023 Annual Research Report
  • [Presentation] 縫合反応/縫合重合: 新規架橋型分子の効率合成法2023

    • Author(s)
      新谷 亮
    • Organizer
      先端有機化学講演会
    • Related Report
      2023 Annual Research Report
    • Invited
  • [Presentation] ラジカル縫合重合による新規環状ポリマーの合成2023

    • Author(s)
      濵田祐介、外川蒼野、新谷 亮
    • Organizer
      第55回有機金属若手の会夏の学校
    • Related Report
      2023 Annual Research Report
  • [Presentation] 縫合反応による新規π共役分子の合成と単分子有機素子としての利用2023

    • Author(s)
      新谷 亮
    • Organizer
      第162回フロンティア材料研究所学術講演会
    • Related Report
      2023 Annual Research Report
    • Invited
  • [Presentation] ラジカル縫合重合の開発による架橋型ポリケトンの合成2023

    • Author(s)
      浜田祐介、外川蒼野、新谷 亮
    • Organizer
      第72回高分子討論会
    • Related Report
      2023 Annual Research Report
  • [Presentation] 拡張π共役分子の迅速合成を可能にするロジウム触媒を用いた縫合反応の開発2023

    • Author(s)
      新谷 亮
    • Organizer
      有機合成化学協会2022年度企業冠賞受賞講演会
    • Related Report
      2023 Annual Research Report
    • Invited
  • [Presentation] Synthesis of New Bridged Polymers by the Stitching Polymerization2023

    • Author(s)
      Ryo Shintani
    • Organizer
      3rd Japanese-Spanish Symposium on Organic Synthesis
    • Related Report
      2023 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] アルケンの異性化を伴う縫合重合による新規ポリ(アリーレンビニレン)の合成2022

    • Author(s)
      外川蒼野、新谷 亮
    • Organizer
      第54回有機金属若手の会夏の学校
    • Related Report
      2022 Research-status Report
  • [Presentation] 縫合重合による新規架橋型ポリマーの合成2022

    • Author(s)
      新谷 亮
    • Organizer
      第71回高分子討論会
    • Related Report
      2022 Research-status Report
    • Invited
  • [Presentation] 縫合重合を用いたポリ(アリーレンビニレン)の合成2022

    • Author(s)
      外川蒼野、新谷 亮
    • Organizer
      第51回複素環化学討論会
    • Related Report
      2022 Research-status Report
  • [Presentation] Rhodium-Catalyzed Stitching Polymerization for the Synthesis of New π-Conjugated Polymers2022

    • Author(s)
      Ryo Shintani
    • Organizer
      The 22nd Tateshina Conference on Organic Chemistry
    • Related Report
      2022 Research-status Report
    • Int'l Joint Research

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Published: 2022-07-05   Modified: 2025-01-30  

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