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Concise synthesis of nanographene by solid-state cross-coupling reaction

Research Project

Project/Area Number 19K15547
Research Category

Grant-in-Aid for Early-Career Scientists

Allocation TypeMulti-year Fund
Review Section Basic Section 33020:Synthetic organic chemistry-related
Research InstitutionHokkaido University

Principal Investigator

Kubota Koji  北海道大学, 化学反応創成研究拠点, 特任助教 (60824828)

Project Period (FY) 2019-04-01 – 2021-03-31
Project Status Completed (Fiscal Year 2020)
Budget Amount *help
¥4,290,000 (Direct Cost: ¥3,300,000、Indirect Cost: ¥990,000)
Fiscal Year 2020: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000)
Fiscal Year 2019: ¥2,340,000 (Direct Cost: ¥1,800,000、Indirect Cost: ¥540,000)
Keywords固体反応 / クロスカップリング / ナノフラフェン / ボールミル / メカノケミストリー / ナノグラフェン
Outline of Research at the Start

ナノグラフェンは、有機ELや有機薄膜太陽電池への応用が期待できる次世代マテリアルであり、その性質は環構造の違いによって大きく変化する。これまで様々な合成法が開発されてきたが、有機合成化学的アプローチによって微細な環構造を精密に制御して合成するボトムアップ合成法に注目が集まっている。しかしながら、既存の方法では原料あるいは生成物が有機溶媒に溶けないという「溶解性問題」を常に考慮する必要があり、分子デザインに大きな制限があった。本研究では、我々が独自に開発した固体内クロスカップリング反応の応用または更なる改良を加え、「溶解性問題」に左右されないナノグラフェンの固相ボトムアップ合成を目指す。

Outline of Final Research Achievements

Nanographenes have attracted attention as next-generation carbon materials, but its molecular design has been severely limited due to the "solubility problem" of its starting materials and products in solvents. In this study, we succeeded in the development of two new reactions with the aim of achieving solid phase synthesis of nanographenes. First, we succeeded in developing Suzuki-Miyaura cross-coupling reactions using ball milling, which proceed efficiently in the solid state. In addition, we found that the solid-state coupling reactions were dramatically accelerated by using a high-temperature ball milling method in which ball milling is performed while heating with a heat gun. This reaction is applicable to insoluble aryl halides and thus we believe that this will be an important tool in nanographene synthesis.

Academic Significance and Societal Importance of the Research Achievements

ナノグラフェンは、次世代カーボンマテリアルとして幅広い応用が期待されている。本研究で新たに開発した固体クロスカップリング反応は、従来の溶液系有機合成反応では困難な不溶性アリールハライドのカップリングを可能とするため、様々な新奇構造を有するナノグラフェンの固相合成に応用されることが期待される。その結果、革新的な機能をもつナノグラフェンの合成が達成され、新たな電子デバイス等の開発が加速することが期待される。

Report

(3 results)
  • 2020 Annual Research Report   Final Research Report ( PDF )
  • 2019 Research-status Report
  • Research Products

    (30 results)

All 2021 2020 2019

All Journal Article (14 results) (of which Int'l Joint Research: 2 results,  Peer Reviewed: 14 results,  Open Access: 2 results) Presentation (13 results) (of which Int'l Joint Research: 8 results,  Invited: 3 results) Patent(Industrial Property Rights) (3 results)

  • [Journal Article] Tackling Solubility Issues in Organic Synthesis: Solid-State Cross-Coupling of Insoluble Aryl Halides2021

    • Author(s)
      Seo Tamae、Toyoshima Naoki、Kubota Koji、Ito Hajime
    • Journal Title

      Journal of the American Chemical Society

      Volume: 143 Issue: 16 Pages: 6165-6175

    • DOI

      10.1021/jacs.1c00906

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] A Copper(I)-Catalyzed Radical-Relay Reaction Enabling the Intermolecular 1,2-Alkylborylation of Unactivated Olefins2021

    • Author(s)
      Akiyama Sota、Oyama Natsuki、Endo Tsubura、Kubota Koji、Ito Hajime
    • Journal Title

      Journal of the American Chemical Society

      Volume: 143 Issue: 13 Pages: 5260-5268

    • DOI

      10.1021/jacs.1c02050

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] A Glove-Box- and Schlenk-Line-Free Protocol for Solid-State C-N Cross-Coupling Reactions Using Mechanochemistry2020

    • Author(s)
      Kubota Koji、Takahashi Rikuro、Uesugi Minami、Ito Hajime
    • Journal Title

      ACS Sustainable Chemistry & Engineering

      Volume: 8 Issue: 44 Pages: 16577-16582

    • DOI

      10.1021/acssuschemeng.0c05834

    • NAID

      120007171677

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Solid‐State Radical C-H Trifluoromethylation Reactions Using Ball Milling and Piezoelectric Materials2020

    • Author(s)
      Pang Yadong、Lee Joo Won、Kubota Koji、Ito Hajime
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 59 Issue: 50 Pages: 22570-22576

    • DOI

      10.1002/anie.202009844

    • NAID

      120007175161

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] General Synthesis of Trialkyl- and Dialkylarylsilylboranes: Versatile Silicon Nucleophiles in Organic Synthesis2020

    • Author(s)
      Shishido, R.; Uesugi, M.; Takahashi, Rikuro.; Mita, T.; Ishiyama, T.; Kubota, K.; Ito, H.
    • Journal Title

      J. Am. Chem. Soc.

      Volume: 142 Issue: 33 Pages: 1412514133-1412514133

    • DOI

      10.1021/jacs.0c03011

    • NAID

      120007132047

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Air- and moisture-stable Xantphos-ligated palladium dialkyl complex as a precatalyst for cross-coupling reactions2020

    • Author(s)
      Takahashi Rina、Kubota Koji、Ito Hajime
    • Journal Title

      Chemical Communications

      Volume: 56 Issue: 3 Pages: 407-410

    • DOI

      10.1039/c9cc06946a

    • NAID

      120006952009

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] Synthesis of Chiral N-Heterocyclic Allylboronates via the Enantioselective Borylative Dearomatization of Pyrroles2020

    • Author(s)
      Hayama Keiichi、Kojima Ryoto、Kubota Koji、Ito Hajime
    • Journal Title

      Organic Letters

      Volume: 22 Issue: 2 Pages: 739-744

    • DOI

      10.1021/acs.orglett.9b04581

    • NAID

      120006953323

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] Copper(I)-Catalyzed Boryl Substitution of 1-Trifluoromethyl Allenes for the Synthesis of 3-Boryl-Substituted 1,1-gem-Difluorodienes2020

    • Author(s)
      Akiyama Sota、Nomura Syogo、Kubota Koji、Ito Hajime
    • Journal Title

      The Journal of Organic Chemistry

      Volume: 85 Issue: 6 Pages: 4172-4181

    • DOI

      10.1021/acs.joc.9b03353

    • NAID

      120006978440

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] Iridium(I)‐Catalyzed C-H Borylation in Air by Using Mechanochemistry2019

    • Author(s)
      Pang Yadong、Ishiyama Tatsuo、Kubota Koji、Ito Hajime
    • Journal Title

      Chemistry - A European Journal

      Volume: 25 Issue: 18 Pages: 4654-4659

    • DOI

      10.1002/chem.201900685

    • NAID

      120006823180

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] Mechanochemistry allows carrying out sensitive organometallic reactions in air: glove-box-and-Schlenk-line-free synthesis of oxidative addition complexes from aryl halides and palladium(0)2019

    • Author(s)
      Kubota Koji、Takahashi Rina、Ito Hajime
    • Journal Title

      Chemical Science

      Volume: 10 Issue: 22 Pages: 5837-5842

    • DOI

      10.1039/c9sc01711a

    • Related Report
      2019 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Synthesis of 2-alkyl-2-boryl-substituted-tetrahydrofurans via copper(i)-catalysed borylative cyclization of aliphatic ketones2019

    • Author(s)
      Kubota Koji、Uesugi Minami、Osaki Shun、Ito Hajime
    • Journal Title

      Organic & Biomolecular Chemistry

      Volume: 17 Issue: 23 Pages: 5680-5683

    • DOI

      10.1039/c9ob00962k

    • NAID

      120006863167

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] Catalytic Enantioselective Synthesis of Allylic Boronates Bearing a Trisubstituted Alkenyl Fluoride and Related Derivatives2019

    • Author(s)
      Akiyama Sota、Kubota Koji、Mikus Malte S.、Paioti Paulo H. S.、Romiti Filippo、Liu Qinghe、Zhou Yuebiao、Hoveyda Amir H.、Ito Hajime
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 58 Issue: 35 Pages: 11998-12003

    • DOI

      10.1002/anie.201906283

    • NAID

      120006880722

    • Related Report
      2019 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Olefin-accelerated C-C cross-coupling reaction in solid-state2019

    • Author(s)
      Seo, T.; Ishiyama, T.; Kubota, K.; Ito, H.
    • Journal Title

      Chem. Sci.

      Volume: 10 Issue: 35 Pages: 8202-8210

    • DOI

      10.1039/c9sc02185j

    • Related Report
      2019 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Redox reactions of small organic molecules using ball milling and piezoelectric materials2019

    • Author(s)
      Kubota Koji、Pang Yadong、Miura Akira、Ito Hajime
    • Journal Title

      Science

      Volume: 366 Issue: 6472 Pages: 1500-1504

    • DOI

      10.1126/science.aay8224

    • NAID

      120006781563

    • Related Report
      2019 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Presentation] メカノケミストリーによる不溶性アリールハライドの固体クロスカップリング反応2021

    • Author(s)
      瀬尾 珠恵、豊島 直喜、久保田 浩司、伊藤 肇
    • Organizer
      日本化学会第101春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] メカノケミストリーで切り拓く未踏ケミカルスペース2020

    • Author(s)
      久保田 浩司
    • Organizer
      京都大学第五回若手ワークショップ
    • Related Report
      2020 Annual Research Report
    • Invited
  • [Presentation] Redox reactions of small organic molecules using ball milling and piezoelectric catalysis2020

    • Author(s)
      Koji Kubota
    • Organizer
      Cooperative phenomena in framework materials: Faraday Discussion
    • Related Report
      2020 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Synthesis of Novel Silylboranes: Versatile Silicon-based Nucleophiles in Organic Synthesis2020

    • Author(s)
      Koji Kubota
    • Organizer
      Zoom Main Group Symposium: From Molecules and Materials
    • Related Report
      2020 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] In Situ Crystallization Enables Selective Monoarylation of Dibromoarenes2020

    • Author(s)
      Tamae Seo, Koji Kubota, Hajime Ito
    • Organizer
      The 6.5th Crystal Engineering and Emerging Materials Workshop of Ontario and Quebec
    • Related Report
      2020 Annual Research Report
    • Int'l Joint Research
  • [Presentation] ボールミルと圧電材料を用いたメカノレドックスの開発2020

    • Author(s)
      Koji Kubota, Yadong Pang, Akira Miura, Hajime Ito
    • Organizer
      日本化学会第100春季年会2020
    • Related Report
      2019 Research-status Report
  • [Presentation] Mechanoredox system for small molecules activation using ball milling2019

    • Author(s)
      Koji Kubota, Yadong Pang, Akira Miura, Hajime Ito
    • Organizer
      2nd ICReDD Internatioanl Symposium -Toward Interdisciplinary Research Guided by Theory and Calculation-
    • Related Report
      2019 Research-status Report
    • Int'l Joint Research
  • [Presentation] メカノケミストリー:機械的な力を利用する有機合成2019

    • Author(s)
      久保田 浩司
    • Organizer
      錯体化学若手の会 北海道地区 第8回勉強会
    • Related Report
      2019 Research-status Report
    • Invited
  • [Presentation] 銅(I)触媒による脱芳香族ホウ素化およびケイ素化2019

    • Author(s)
      久保田 浩司・羽山 慶一・高橋 陸朗・小島 遼人・伊藤 肇
    • Organizer
      第23回ケイ素化学協会シンポジウム
    • Related Report
      2019 Research-status Report
  • [Presentation] Mechano-Redox Activation: Arylation and Borylation Promoted by Mechanical Force2019

    • Author(s)
      Koji Kubota
    • Organizer
      The 14th International Conference on Cutting-Edge Organic Synthesis in Asia
    • Related Report
      2019 Research-status Report
    • Int'l Joint Research
  • [Presentation] Olefin-accelerated C-N cross-coupling in the solid-state2019

    • Author(s)
      Koji Kubota, Tamae Seo, Katsumasa Koide, Yasuchika Hasegawa, Hajime Ito
    • Organizer
      ACS Fall 2019 National Meeting & Exposition 2019
    • Related Report
      2019 Research-status Report
    • Int'l Joint Research
  • [Presentation] Mechanochemical C-H Borylation in Air2019

    • Author(s)
      Koji Kubota
    • Organizer
      The 47th Naito Conference on C-H Bond Activation and Transformation
    • Related Report
      2019 Research-status Report
    • Int'l Joint Research
  • [Presentation] Mechanochemistry enables solid-state cross-coupling reactions2019

    • Author(s)
      Koji Kubota
    • Organizer
      Hokkaido Summer Symposium 2019 on Catalysis for Organic Synthesis
    • Related Report
      2019 Research-status Report
    • Int'l Joint Research
  • [Patent(Industrial Property Rights)] 脱離基を有するモノクロスカップリング芳香族化合物の製造方法2020

    • Inventor(s)
      伊藤肇、久保田浩司
    • Industrial Property Rights Holder
      伊藤肇、久保田浩司
    • Industrial Property Rights Type
      特許
    • Filing Date
      2020
    • Related Report
      2019 Research-status Report
  • [Patent(Industrial Property Rights)] 圧電材料を利用するメカノレドックス反応及びその反応を用いる製造方法2019

    • Inventor(s)
      伊藤肇、久保田浩司
    • Industrial Property Rights Holder
      伊藤肇、久保田浩司
    • Industrial Property Rights Type
      特許
    • Filing Date
      2019
    • Related Report
      2019 Research-status Report
  • [Patent(Industrial Property Rights)] 溶媒を使用しないクロスカップリング反応及びその反応を用いる製造方法2019

    • Inventor(s)
      伊藤肇、久保田浩司
    • Industrial Property Rights Holder
      伊藤肇、久保田浩司
    • Industrial Property Rights Type
      特許
    • Filing Date
      2019
    • Acquisition Date
      2020
    • Related Report
      2019 Research-status Report

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Published: 2019-04-18   Modified: 2022-01-27  

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