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Developing open-shell molecular structures of high-energy and novel spin-functional unit by use of elementary particle muons

Research Project

Project/Area Number 19H02685
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Review Section Basic Section 32020:Functional solid state chemistry-related
Research InstitutionTokyo Institute of Technology

Principal Investigator

Ito Shigekazu  東京工業大学, 物質理工学院, 准教授 (00312538)

Project Period (FY) 2019-04-01 – 2023-03-31
Project Status Completed (Fiscal Year 2022)
Budget Amount *help
¥17,420,000 (Direct Cost: ¥13,400,000、Indirect Cost: ¥4,020,000)
Fiscal Year 2022: ¥2,990,000 (Direct Cost: ¥2,300,000、Indirect Cost: ¥690,000)
Fiscal Year 2021: ¥2,990,000 (Direct Cost: ¥2,300,000、Indirect Cost: ¥690,000)
Fiscal Year 2020: ¥2,990,000 (Direct Cost: ¥2,300,000、Indirect Cost: ¥690,000)
Fiscal Year 2019: ¥8,450,000 (Direct Cost: ¥6,500,000、Indirect Cost: ¥1,950,000)
Keywordsラジカル / 素粒子 / ミュオン / ミュオニウム / 有機合成化学 / 複素環 / 複素環構造 / イミドイルラジカル / ミュオン科学 / 有機合成 / 結晶構造 / リン複素環 / 合成化学 / 素粒子科学 / ヘテロ元素 / 複素環化合物 / フッ素
Outline of Research at the Start

ミュオンはプロトンの1/9の質量をもつスピン I=1/2 の素粒子で、加速器から発生させて有機分子に打ち込むと、エネルギーを減少させながら電子を捕獲して「軽い水素原子」に相当するミュオニウムに変化する。本研究では、高周期元素を含む縮環共役化合物とフルオロアルキル置換ホウ素化合物のミュオニウム付加反応に着目し、通常の化学的手法では同定の難しい未知の高エネルギー開殻分子構造を同定する。続いて、新たに見出された開殻分子構造を有する、単離可能な化合物を合成する手法の開拓に挑む。さらに、このように得られた知見をもとに新しいスピン機能分子ユニットを創製し、分子スピントロニクスや医薬品開発などに展開する。

Outline of Final Research Achievements

In this project, we attempted generating unusual paramagnetic species by utilizing muoniums which were formed from muon and electron. Muons are produced by proton accelerators, and the muonium can provide novel molecular structures that cannot be prepared by usual chemical methods. At first, we confirmed addition of muonium to the phosphorus heterocycles of singlet biradicals suggesting that the regioselectivity would remarkably correlate with the electronic properties and the crystal structures. Next, we characterized the regioselective muoniation to the phosphorus analog of anthracene together with the unprecedented quasi-stable conjugated system which was induced by the muon isotope effect. In addition, we succeeded in observing an imidoyl radical by using muonium first time, and produced particular paramagnetic pai-conjugated structures from the heavier carbonyl compounds.

Academic Significance and Societal Importance of the Research Achievements

本研究の成果は、有機合成化学とミュオンをうまく組み合わせることによって前例のない開殻分子構造を創り出せることを明確に証明した。ミュオンの高エネルギー状態は、通常では不安定で生成できない開殻共役系分子構造などを与えるだけでなく、分子の物性に強く相関した情報も得られる。空間的にも時間的にも分子創成の可能性を飛躍的に向上させることが可能となり、前衛的な物質科学の展開がこれから大いに期待される。

Report

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

    (47 results)

All 2023 2022 2021 2020 2019 Other

All Int'l Joint Research (4 results) Journal Article (16 results) (of which Int'l Joint Research: 3 results,  Peer Reviewed: 14 results,  Open Access: 3 results) Presentation (24 results) (of which Int'l Joint Research: 3 results,  Invited: 5 results) Remarks (3 results)

  • [Int'l Joint Research] TRIUMF/The University of British Columbia(カナダ)

    • Related Report
      2022 Annual Research Report
  • [Int'l Joint Research] TRIUMF/University of British Columbia(カナダ)

    • Related Report
      2021 Annual Research Report
  • [Int'l Joint Research] TRIUMF/University of British Columbia(カナダ)

    • Related Report
      2020 Annual Research Report
  • [Int'l Joint Research] TRIUMF(カナダ)

    • Related Report
      2019 Annual Research Report
  • [Journal Article] Copper‐Catalyzed Enantioselective Hydrosilylation of gem‐Difluorocyclopropenes Leading to a Stereochemical Study of the Silylated gem‐Difluorocyclopropanes2022

    • Author(s)
      Sekine Keisuke、Akaishi Dai、Konagaya Kakeru、Ito Shigekazu
    • Journal Title

      Chemistry - A European Journal

      Volume: 28 Issue: 32

    • DOI

      10.1002/chem.202200657

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Muon Spin Rotation/Resonance (μSR) for Studying Radical Reactivity of Unsaturated Organophosphorus Compounds2022

    • Author(s)
      Ito Shigekazu
    • Journal Title

      Chemistry - A European Journal

      Volume: 28 Issue: 53

    • DOI

      10.1002/chem.202200843

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] リン複素環分子の素粒子ラジカル反応2022

    • Author(s)
      伊藤繁和
    • Journal Title

      月刊「細胞」

      Volume: 54 Pages: 518-522

    • Related Report
      2022 Annual Research Report
  • [Journal Article] Gold(I) Complexation of Phosphanoxy‐Substituted Phosphaalkenes for Activation‐Free LAuCl Catalysis2021

    • Author(s)
      Kato Miki、Ueta Yasuhiro、Ito Shigekazu
    • Journal Title

      Chemistry - A European Journal

      Volume: 27 Issue: 7 Pages: 2469-2475

    • DOI

      10.1002/chem.202004281

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] TiCl4‐Mediated [2+2] Cycloaddition for Synthesis of Isolable CF3‐Substituted 2‐Azetines2021

    • Author(s)
      Hara Shunya、Ito Shigekazu
    • Journal Title

      Asian Journal of Organic Chemistry

      Volume: 10 Issue: 4 Pages: 788-792

    • DOI

      10.1002/ajoc.202100082

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Muonium Addition to a peri‐Trifluoromethylated 9‐Phosphaanthracene Producing a High‐Energy Paramagnetic π‐Conjugated Fused Heterocycle2021

    • Author(s)
      Koshino Kota、Kojima Kenji M.、McKenzie Iain、Ito Shigekazu
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 60 Issue: 45 Pages: 24034-24038

    • DOI

      10.1002/anie.202109784

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Muonium Addition to the Radicalic Carbon in 1,3-Diphosphacyclobutane-2,4-diyl2021

    • Author(s)
      Ito Shigekazu、Akama Hikaru、Ueta Yasuhiro、McKenzie Iain、Kojima Kenji M.
    • Journal Title

      Bulletin of the Chemical Society of Japan

      Volume: 94 Issue: 12 Pages: 2970-2972

    • DOI

      10.1246/bcsj.20210352

    • NAID

      130008144742

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Diels-Alder reactions of 1-phosphabutadienes: a highly selective route to P=C-substituted phosphacyclohexenes2020

    • Author(s)
      K. Ohtsuki, H. T. G. Walsgrove, Y. Hayashi, S. Kawauchi, B. O. Patrick, D. P. Gates, S. Ito
    • Journal Title

      Chem. Commun.

      Volume: 56 Issue: 5 Pages: 774-777

    • DOI

      10.1039/c9cc08997g

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Scalable Orbital Tuning of the 1,3-Diphosphacyclobutane-2,4-diyl Unit of Singlet Biradicaloid2020

    • Author(s)
      Y. Ueta, S. Ito
    • Journal Title

      J. Org. Chem.

      Volume: 85 Issue: 22 Pages: 14384-14390

    • DOI

      10.1021/acs.joc.0c00512

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Convenient Preparation and Structure Determination of Air- and Moisture-Tolerant Difluoromethylborates2020

    • Author(s)
      A. Yokawa, S. Ito
    • Journal Title

      Chem. Asian J.

      Volume: 15 Issue: 21 Pages: 3432-3436

    • DOI

      10.1002/asia.202000854

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Investigation of Organic Molecules Using Elementary Subatomic Particle: Muon Spin Spectroscopy for Reaction Analysis of the Open-Shell Singlet Heterocycle2019

    • Author(s)
      伊藤繁和
    • Journal Title

      Journal of Synthetic Organic Chemistry, Japan

      Volume: 77 Issue: 8 Pages: 800-812

    • DOI

      10.5059/yukigoseikyokaishi.77.800

    • NAID

      130007689062

    • ISSN
      0037-9980, 1883-6526
    • Year and Date
      2019-08-01
    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Incomplete Electrocyclization of a Sterically Hindered 1,4‐Diphosphabutadiene2019

    • Author(s)
      Shinozaki Tomokazu、Rosas‐Sanchez Alfredo、Hashizume Daisuke、Ito Shigekazu
    • Journal Title

      ChemPlusChem

      Volume: 84 Issue: 11 Pages: 1761-1766

    • DOI

      10.1002/cplu.201900632

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Muon spin rotation (muSR) study of a sterically encumbered thioaldehyde2019

    • Author(s)
      Shigekazu Ito, Naoto Kato, Yasuhiro Ueta, Koichi Mikami, Kenji M. Kojima
    • Journal Title

      Phosphorus, Sulfur, and Silicon, and the Related Elements

      Volume: 194 Issue: 7 Pages: 735-738

    • DOI

      10.1080/10426507.2019.1603719

    • Related Report
      2019 Annual Research Report
  • [Journal Article] Synthetic Methodologies for Perfluoroaryl-Substituted (Diaryl)methylphosphonates, -Phosphinates via SNAr Reaction2019

    • Author(s)
      Kohei Fujii, Shigekazu Ito, Koichi Mikami
    • Journal Title

      J. Org. Chem.

      Volume: 84 Issue: 19 Pages: 12281-12291

    • DOI

      10.1021/acs.joc.9b01402

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Design of Phosphinic Acid Catalysts with the Closest Stereogenicity at the α-Position: Synthesis and Application of α-Stereogenic Perfluoroalkyl Phosphinic Acid Catalysts2019

    • Author(s)
      Kohei Fujii, Haruki Todani, Shigekazu Ito, Koichi Mikami
    • Journal Title

      Org. Lett.

      Volume: 21 Issue: 9 Pages: 3387-3391

    • DOI

      10.1021/acs.orglett.9b01131

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Regiocontrolled Heptafluoroisopropylation of Aromatic Halides by Copper(I) Carboxylates with Heptafluoroisopropyl-Zinc Reagents2019

    • Author(s)
      Soichiro Ono, Yuki Yokota, Shigekazu Ito, Koichi Mikami
    • Journal Title

      Org. Lett.

      Volume: 21 Issue: 4 Pages: 1093-1097

    • DOI

      10.1021/acs.orglett.8b04147

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Presentation] イソニトリルへのミュオニウム付加:イミドイルラジカル生成のmuSR観測2023

    • Author(s)
      伊藤繁和, 小長谷翔, Reuben Parchment-Morrison, 小嶋健児, Iain McKenzie
    • Organizer
      日本化学会第103春季年会
    • Related Report
      2022 Annual Research Report
  • [Presentation] 経路積分分子動力学法を用いたミューオニウム化キサンテンチオ ンの同族元素効果2023

    • Author(s)
      桑畑 和明、伊藤 繁和、立川 仁典
    • Organizer
      日本化学会第103春季年会
    • Related Report
      2022 Annual Research Report
  • [Presentation] ミューオニウム化キサンテンチオンのHFCCに対する量子効果2022

    • Author(s)
      桑畑 和明、伊藤 繁和、立川 仁典
    • Organizer
      日本コンピュータ化学会2022年春季年会
    • Related Report
      2022 Annual Research Report
  • [Presentation] Study on LAuCl catalysis using the P-ligand bearing pseudo-coordinative P=C2022

    • Author(s)
      ITO Shigekazu, KATO Miki, ISHIHARA Keisuke, UETA Yasuhiro
    • Organizer
      Gold2022
    • Related Report
      2022 Annual Research Report
    • Int'l Joint Research
  • [Presentation] 経路積分分子動力学法を用いたミューオニウム化キサンテンチオンの理論研究2022

    • Author(s)
      桑畑 和明、伊藤 繁和、立川 仁典
    • Organizer
      第16回分子科学討論会
    • Related Report
      2022 Annual Research Report
  • [Presentation] muLCRによるチオジベンゾスベレノンのMuラジカル反応解析2022

    • Author(s)
      伊藤 繁和、赤間ひかる、中村 淳平、西村昇一郞、幸田 章宏
    • Organizer
      第32回基礎有機化学討論会
    • Related Report
      2022 Annual Research Report
  • [Presentation] CF2Hボレートの酸化を経由する新規ジフルオロメチル化反応の開拓2022

    • Author(s)
      小長谷翔、伊藤繁和
    • Organizer
      第121回有機合成シンポジウム
    • Related Report
      2022 Annual Research Report
  • [Presentation] シリル置換gem-ジフルオロシクロプロパンの触媒的不斉合成と脱シリル化における立体化学の変化2022

    • Author(s)
      赤石大、関根圭亮、小長谷翔、伊藤繁和
    • Organizer
      第121回有機合成シンポジウム
    • Related Report
      2022 Annual Research Report
  • [Presentation] P=Cホスフィンの遠隔効果を利用した 不斉金触媒反応の開発2022

    • Author(s)
      石原啓介、伊藤繁和
    • Organizer
      第83回有機合成化学協会関東支部シンポジウム
    • Related Report
      2022 Annual Research Report
  • [Presentation] リン複素環化合物の素粒子ラジカル反応2022

    • Author(s)
      伊藤繁和
    • Organizer
      第49回有機典型元素化学討論会
    • Related Report
      2022 Annual Research Report
    • Invited
  • [Presentation] Radical Reactions of Phosphorus Heterocycles with Muonium2022

    • Author(s)
      Shigekazu Ito
    • Organizer
      11th Singapore International Chemistry Conference (SICC-11)
    • Related Report
      2022 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] 有機化学とミュオン分光を組みあわせた物質科学研究2021

    • Author(s)
      伊藤 繁和
    • Organizer
      大つくば物理化学セミナー
    • Related Report
      2021 Annual Research Report
    • Invited
  • [Presentation] 素粒子ミュオンを用いたMes*チオホルムアミドのラジカル反応解析2021

    • Author(s)
      赤間 ひかる、小嶋 健児、 Iain McKenzie、伊藤 繁和
    • Organizer
      第81回有機合成化学協会関東支部シンポジウム
    • Related Report
      2021 Annual Research Report
  • [Presentation] 素粒子を用いたフルオロアルキル置換9-ホスファアントラセンのラジカル反応解析2021

    • Author(s)
      伊藤 繁和,、越野 皓太、 小嶋 健児、 Iain McKenzie
    • Organizer
      第31回基礎有機化学討論会
    • Related Report
      2021 Annual Research Report
  • [Presentation] CF2Hボレートを用いる鈴木-宮浦反応の 開発研究2021

    • Author(s)
      小長谷 翔、伊藤 繁和
    • Organizer
      第790回有機合成化学協会関東支部シンポジウム
    • Related Report
      2021 Annual Research Report
  • [Presentation] P-アリール置換リン複素環ビラジカルのミュオンスピン分光解析2021

    • Author(s)
      伊藤 繁和、植田 恭弘、赤間ひかる、小嶋 健児、Iain McKenzie
    • Organizer
      日本化学会第101春季年会
    • Related Report
      2021 Annual Research Report
  • [Presentation] シリカート中間体を経由するジフルオロメチルボレートの合成と誘導化2020

    • Author(s)
      余川晃崇、伊藤繁和
    • Organizer
      第47回有機典型元素化学討論会
    • Related Report
      2020 Annual Research Report
  • [Presentation] ボロン酸エステルを用いるジフルオロメチルホウ素導入剤の開発2020

    • Author(s)
      余川晃崇、伊藤繁和
    • Organizer
      日本化学会第100春季年会(新型コロナウイルスのため中止)
    • Related Report
      2020 Annual Research Report
  • [Presentation] SNArによるペルフルオロアリール基を導入したホスファアルケンの合成2020

    • Author(s)
      大月一晃、伊藤繁和
    • Organizer
      日本化学会第100春季年会(新型コロナウイルスのため中止)
    • Related Report
      2020 Annual Research Report
  • [Presentation] ジフォスファシクロブタンビラジカルへのミュオニウム付加反応の解明2020

    • Author(s)
      伊藤繁和
    • Organizer
      日本中間子科学会 総会
    • Related Report
      2020 Annual Research Report
    • Invited
  • [Presentation] 銅触媒を用いる芳香族ヘプタフルオロイソプロピル化反応の開発と 電子機能性物質の創製研究2019

    • Author(s)
      小野 総一郎、横田 有生、伊藤 繁和、三上 幸一
    • Organizer
      第115回有機合成シンポジウム
    • Related Report
      2019 Annual Research Report
  • [Presentation] Muon Spin Spectroscopy for Chemistry of the P-Heterocyclic Singlet Biradicals2019

    • Author(s)
      Shigekazu Ito, Yasuhiro Ueta, Kota Koshino, Koichi Mikami, Kenji M. Kojima, Iain McKenzie
    • Organizer
      The 13th International Conference on Heteroatom Chemistry (ICHAC 2019)
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research
  • [Presentation] ミュオンスピン分光法による開殻一重項複素環分子の反応解析2019

    • Author(s)
      伊藤繁和
    • Organizer
      有機化学コロキウム2019
    • Related Report
      2019 Annual Research Report
    • Invited
  • [Presentation] ハロゲンを有する1-ホスファブタジエンの触媒的合成と新規[4+2]二量化反応の解析2019

    • Author(s)
      大月一晃、林慶浩、川内進、伊藤繁和
    • Organizer
      第46回有機典型元素化学討論会
    • Related Report
      2019 Annual Research Report
  • [Remarks] 素粒子ミュオンを用いた高エネルギー複素環ラジカルの創成

    • URL

      https://www.titech.ac.jp/news/2021/061725

    • Related Report
      2021 Annual Research Report
  • [Remarks] It's Elementary:

    • URL

      https://www.titech.ac.jp/english/news/2021/061737

    • Related Report
      2021 Annual Research Report
  • [Remarks]

    • URL

      http://www.apc.titech.ac.jp/~sito/index-e.html

    • Related Report
      2019 Annual Research Report

URL: 

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

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