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Chemical synthesis of diatomic carbon (C2) with hypervalent halogen(III) reagents and its application

Research Project

Project/Area Number 18K19068
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 InstitutionThe University of Tokyo

Principal Investigator

Miyamoto Kazunori  東京大学, 大学院薬学系研究科(薬学部), 准教授 (40403696)

Project Period (FY) 2018-06-29 – 2021-03-31
Project Status Completed (Fiscal Year 2020)
Budget Amount *help
¥6,370,000 (Direct Cost: ¥4,900,000、Indirect Cost: ¥1,470,000)
Fiscal Year 2020: ¥1,040,000 (Direct Cost: ¥800,000、Indirect Cost: ¥240,000)
Fiscal Year 2019: ¥1,170,000 (Direct Cost: ¥900,000、Indirect Cost: ¥270,000)
Fiscal Year 2018: ¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000)
Keywords炭素同素体 / 二原子炭素 / ヨウ素 / 超原子価 / 反応機構 / 超原子価ヨウ素 / フラーレン / カーボンナノチューブ / ラジカル / グラフェン / グラファイト / 四重結合 / ハロゲン
Outline of Final Research Achievements

Diatomic carbon (C2) is historically an elusive chemical species. It has long been believed that the generation of C2 requires extremely high physical energy, such as an electric carbon arc or multiple photon excitation, and so it has been the general consensus that the inherent nature of C2 in the ground state is experimentally inaccessible. Here, we present the chemical synthesis of C2 from a hypervalent alkynyliodane(III) in a flask at room temperature or below, providing experimental evidence to support theoretical predictions that C2 has a singlet biradical character with a quadruple bond, thus settling a long-standing controversy between experimental and theoretical chemists, and that C2 serves as a molecular element in the bottom-up chemical synthesis of nanocarbons such as graphite, carbon nanotubes, and C60.

Academic Significance and Societal Importance of the Research Achievements

今回の新しい反応を実現することにより、これまで発生方法が過酷な条件(3500℃以上の高温下等)に限られていたため、性質が謎に包まれていた基底状態のC2のユニークな物理化学的性質を明らかにすることができました。これには炭素では初めての四重結合性を証明できたことが含まれており、化学の教科書に新しい1ペー ジを書き加えることができる成果です。また本研究を通じて、これまで機構が不明であった炭素同素体の生成機構の一部が明らかになり、炭素の材料科学への新しいアプローチを提供できたという観点でも意義深いと考えられます。

Report

(4 results)
  • 2020 Annual Research Report   Final Research Report ( PDF )
  • 2019 Research-status Report
  • 2018 Research-status Report
  • Research Products

    (44 results)

All 2021 2020 2019 2018

All Journal Article (20 results) (of which Int'l Joint Research: 1 results,  Peer Reviewed: 20 results,  Open Access: 7 results) Presentation (23 results) (of which Int'l Joint Research: 1 results,  Invited: 2 results) Patent(Industrial Property Rights) (1 results)

  • [Journal Article] Hypervalent Organo-λ<sup>3</sup>-chloranes2021

    • Author(s)
      Kazunori Miyamoto, Masanobu Uchiyama
    • Journal Title

      Chemistry Letters

      Volume: 50 Issue: 4 Pages: 832-838

    • DOI

      10.1246/cl.200849

    • NAID

      130008025775

    • ISSN
      0366-7022, 1348-0715
    • Year and Date
      2021-04-05
    • Related Report
      2020 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Reply to “A Thermodynamic assessment of the reported room-temperature chemical synthesis of C2”2021

    • Author(s)
      Miyamoto Kazunori、Narita Shodai、Masumoto Yui、Hashishin Takahiro、Osawa Taisei、Kimura Mutsumi、Ochiai Masahito、Uchiyama Masanobu
    • Journal Title

      Nature Communications

      Volume: 12 Issue: 1 Pages: 1245-1245

    • DOI

      10.1038/s41467-021-21439-2

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Illuminating Stannylation2021

    • Author(s)
      Sakamoto Kyoka、Nagashima Yuki、Wang Chao、Miyamoto Kazunori、Tanaka Ken、Uchiyama Masanobu
    • Journal Title

      Journal of the American Chemical Society

      Volume: 143 Issue: 15 Pages: 5629-5635

    • DOI

      10.1021/jacs.1c00887

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] α‐Cyclodextrin Encapsulation of Bicyclo[1.1.1]pentane Derivatives: A Storable Feedstock for Preparation of [1.1.1]Propellane2021

    • Author(s)
      Matsunaga Tadafumi、Kanazawa Junichiro、Ichikawa Tomohiro、Harada Mei、Nishiyama Yusuke、Duong Nghia Tuan、Matsumoto Takashi、Miyamoto Kazunori、Uchiyama Masanobu
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 60 Issue: 5 Pages: 2578-2582

    • DOI

      10.1002/anie.202014997

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Facile Preparation of 1-Hydroxy-1,2-Benziodoxol-3(1H)-One 1-Oxide (IBX) and Dess-Martin Reagent Using Sodium Hypochlorite under Carbon Dioxide2021

    • Author(s)
      K. Miyamoto, T. Okada, T. Toyama, S. Imamura, M. Uchiyama
    • Journal Title

      Heterocycles

      Volume: 103 Issue: 2 Pages: 694-694

    • DOI

      10.3987/com-20-s(k)66

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Boron-vertex modification of carba-closo-dodecaborate for high-performance magnesium-ion battery electrolyte2021

    • Author(s)
      Watanabe Mamoru、Kanazawa Junichiro、Hamamura Tomofumi、Shimokawa Takumi、Miyamoto Kazunori、Hibino Mitsuhiro、Nakura Kensuke、Inatomi Yuu、Kitazawa Yu、Uchiyama Masanobu
    • Journal Title

      Materials Advances

      Volume: 2 Issue: 3 Pages: 937-941

    • DOI

      10.1039/d0ma00925c

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] DFT Study of a Missing Piece in Brasilane-Type Structure Biosynthesis: An Unusual Skeletal Rearrangement2020

    • Author(s)
      Sato Hajime、Hashishin Takahiro、Kanazawa Junichiro、Miyamoto Kazunori、Uchiyama Masanobu
    • Journal Title

      Journal of the American Chemical Society

      Volume: 142 Issue: 47 Pages: 19830-19834

    • DOI

      10.1021/jacs.0c09616

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Nucleophilic Diboration Strategy Targeting Diversified 1‐Boraphenarene Architectures2020

    • Author(s)
      Hirano Keiichi、Morimoto Kensuke、Fujioka Shota、Miyamoto Kazunori、Muranaka Atsuya、Uchiyama Masanobu
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 59 Issue: 48 Pages: 21448-21453

    • DOI

      10.1002/anie.202009242

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Room-temperature Chemical Synthesis of C22020

    • Author(s)
      Kazunori Miyamoto, Shodai Narita, Yui Masumoto, Takahiro Hashishin, Taisei Osawa, Mutsumi Kimura, Masahito Ochiai, Masanobu Uchiyama
    • Journal Title

      Nature Communcations

      Volume: 11 Issue: 1 Pages: 2134-2134

    • DOI

      10.1038/s41467-020-16025-x

    • Related Report
      2019 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] BF3-Catalyzed Skeletal Rearrangement of 7-En-2-ynones to endo-Type Cyclic Dienes2020

    • Author(s)
      Daisuke Sato, Yuichiro Watanabe, Keiichi Noguchi, Junichiro Kanazawa, Kazunori Miyamoto, Masanobu Uchiyama
    • Journal Title

      Organic Letters

      Volume: - Issue: 11 Pages: 4063-4067

    • DOI

      10.1021/acs.orglett.0c00949

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] Rhodium-Catalyzed Highly Diastereo- and Enantioselective Synthesis of A Configurationally Stable S-Shaped [11]Helicene-Like Molecule2020

    • Author(s)
      Suzuka Kinoshita, Ryota Yamano, Yu Shibata, Yusuke Tanaka, Takashi Matsumoto, Kazunori Miyamoto, Atsuya Muranaka, Masanobu Uchiyama, Ken Tanaka
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 59 Issue: 27 Pages: 11020-11027

    • DOI

      10.1002/anie.202001794

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] Practical Synthesis of Ethynyl(phenyl)-λ3-iodane Using Calcium Carbide as an Ethynyl Group Source2020

    • Author(s)
      Takahiro Hashishin, Taisei Osawa, Kazunori Miyamoto, Masanobu Uchiyama
    • Journal Title

      Frontiers in Chemistry

      Volume: 8 Pages: 12-16

    • DOI

      10.3389/fchem.2020.00012

    • Related Report
      2019 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Chennat-Type Synthesis of 1,4-Dihydropyridine Derivatives in Water: Role of a Hydrogen-Bonding Network2020

    • Author(s)
      Shigeki Isomura, Mayu Anzai, Chieka Kobayashi, Yoshinori Okuno, Kazunori Miyamoto, Masanobu Uchiyama, Yasuo Sato
    • Journal Title

      ChemistrySelect

      Volume: 5 Issue: 6 Pages: 2075-2077

    • DOI

      10.1002/slct.201904144

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] Lipshutz-type Bis(amido)argentate for Directed ortho Argentation2020

    • Author(s)
      Noriyuki Tezuka, Keiichi Hirano, Andrew J. Peel, Andrew E. H. Wheatley, Kazunori Miyamoto, Masanobu Uchiyama
    • Journal Title

      Chemical Sciences

      Volume: 11 Issue: 7 Pages: 1855-1861

    • DOI

      10.1039/c9sc06060j

    • Related Report
      2019 Research-status Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Diaryl-λ3-chloranes: Versatile Synthesis and Unique Reactivity as Aryl Cation Equivalent2019

    • Author(s)
      Nakajima Misuzu、Miyamoto Kazunori、Hirano Keiichi、Uchiyama Masanobu
    • Journal Title

      Journal of the American Chemical Society

      Volume: 141 Issue: 16 Pages: 6499-6503

    • DOI

      10.1021/jacs.9b02436

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] N-Alkynylpyridinium Salts: Highly Electrophilic Alkyne?Pyridine Conjugates as Precursors of Cationic Nitrogen-Embedded Polycyclic Aromatic Hydrocarbons2018

    • Author(s)
      Toriumi Naoyuki、Asano Norihito、Miyamoto Kazunori、Muranaka Atsuya、Uchiyama Masanobu
    • Journal Title

      J. Am. Chem. Soc.

      Volume: 140 Issue: 11 Pages: 3858-3862

    • DOI

      10.1021/jacs.8b00356

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Journal Article] Stable Thiele’s Hydrocarbon Derivatives Exhibiting Near-Infrared Absorption/Emission and Two-Step Electrochromism2018

    • Author(s)
      Yuta Okamoto, Masaru Tanioka, Atsuya Muranaka, Kazunori Miyamoto, Tetsuya Aoyama, Xingmei Ouyang, Shinichiro Kamino, Daisuke Sawada, Masanobu Uchiyama
    • Journal Title

      J. Am. Chem. Soc.

      Volume: 140 Issue: 51 Pages: 17857-17861

    • DOI

      10.1021/jacs.8b11092

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Journal Article] Safer Synthesis of (Diacetoxyiodo)arenes using Sodium Hypochlorite Pentahydrate (NaClO-5H2O)2018

    • Author(s)
      Ayumi Watanabe, Kazunori Miyamoto, Tomohide Okada, Tomotake Asawa, and Masanobu Uchiyama
    • Journal Title

      J. Org. Chem.

      Volume: 83 Issue: 23 Pages: 14262-14268

    • DOI

      10.1021/acs.joc.8b02541

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Journal Article] Oxidative α‐Acetoxylation of a β‐Oxime Ester with (Diacetoxyiodo)benzene Catalyzed by ScIII Salts: An Approach to the Docetaxel Side Chain2018

    • Author(s)
      Kazunori Miyamoto, Md. Mahbubul Hoque, Yuhki Senoh, Mohammad Idrish Ali, Hisao Nemoto, Tadakatsu Mandai
    • Journal Title

      Eur. J. Org. Chem.

      Volume: - Issue: 22 Pages: 2841-2845

    • DOI

      10.1002/ejoc.201800292

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Journal Article] Chemistry of Hypervalent Bromine2018

    • Author(s)
      Kazunori Miyamoto
    • Journal Title

      PATAI'S Chemistry of Functional Groups

      Volume: - Pages: 1-25

    • DOI

      10.1002/9780470682531.pat0956

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Presentation] 3価の超原子価ビニルクロランの合成とその反応2021

    • Author(s)
      渡邊 勇一郎、高木 泰成、宮本 和範、内山 真伸
    • Organizer
      日本薬学会第141年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] 隣接基関与による安定化を活用した三価の超原子価臭素化合物の合成と反応2021

    • Author(s)
      髙木 泰成、齊藤 基道、辻 俊輔、落合 正仁、宮本 和範、内山 真伸
    • Organizer
      日本薬学会第141年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] 三価の超原子価ヨウ素試薬を用いた嵩高い脂肪族カルボン酸の脱炭酸臭素化反応2021

    • Author(s)
      小山田 健太、渡辺 歩実、宮本 和範、内山 真伸
    • Organizer
      日本薬学会第141年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] アルキニルヨーダンを用いた二原子炭素の発生を鍵とする炭素材料形成反応2020

    • Author(s)
      橋新 崇広、大澤 泰生、成田 将大、増本 優衣、宮本 和範、内山 真伸
    • Organizer
      日本薬学会第140年会
    • Related Report
      2019 Research-status Report
  • [Presentation] 三価のビニルクロランの合成とその有用性2020

    • Author(s)
      渡邊 勇一郎、高木 泰成、宮本 和範、内山 真伸
    • Organizer
      日本薬学会第140年会
    • Related Report
      2019 Research-status Report
  • [Presentation] 超原子価ヨウ素試薬を用いた脂肪族カルボン酸の脱炭酸臭素化反応2020

    • Author(s)
      小山田 健太、渡辺 歩実、宮本 和範、内山 真伸
    • Organizer
      日本薬学会第140年会
    • Related Report
      2019 Research-status Report
  • [Presentation] イミノヨーダンの添加剤フリーな調製法と有機合成への応用2020

    • Author(s)
      森崎 郁弥、馬場 崇史、宮本 和範、内山 真伸、齊藤 亜紀夫
    • Organizer
      日本薬学会第140年会
    • Related Report
      2019 Research-status Report
  • [Presentation] 超原子価有機ハロゲン化合物を活用する炭素反応活性種の発生とその反応2020

    • Author(s)
      宮本和範
    • Organizer
      日本薬学会第140年会
    • Related Report
      2019 Research-status Report
    • Invited
  • [Presentation] カルボランアニオンを基盤とした新規骨格を有する弱配位性アニオン種の合成とその性能評価2019

    • Author(s)
      渡部衛,北沢裕,宮本和範,金澤純一朗,内山真伸
    • Organizer
      第45回反応と合成の進歩シンポジウム
    • Related Report
      2019 Research-status Report
  • [Presentation] 超原子価アルキニルヨーダンを活用した常温・常圧における炭素材料合成法の開発2019

    • Author(s)
      橋新崇広, 宮本和範, 内山真伸
    • Organizer
      第9回CSJ化学フェスタ
    • Related Report
      2019 Research-status Report
  • [Presentation] PhI(OAc)2 と KBr を用いた高歪み/嵩高いカルボン酸の効率的脱炭酸臭素化反応2019

    • Author(s)
      小山田健太, 渡辺歩実, 宮本和範, 内山真伸
    • Organizer
      第9回CSJ化学フェスタ
    • Related Report
      2019 Research-status Report
  • [Presentation] 安定なビニルクロランの合成、構造とその反応性2019

    • Author(s)
      渡邊勇一郎, 高木泰成, 宮本和範, 内山真伸
    • Organizer
      第9回CSJ化学フェスタ
    • Related Report
      2019 Research-status Report
  • [Presentation] ジアリール塩素(III)を活用した求電子的アリール化反応2019

    • Author(s)
      中島 美涼、宮本 和範、内山 真伸
    • Organizer
      日本薬学会第139年会
    • Related Report
      2018 Research-status Report
  • [Presentation] 次亜塩素酸ナトリウム5水和物を用いたジアセトキシヨードアレーンの実用的合成法の開発2019

    • Author(s)
      渡辺 歩実、宮本 和範、内山 真伸
    • Organizer
      日本薬学会第139年会
    • Related Report
      2018 Research-status Report
  • [Presentation] 超原子価ジアセトキシヨードベンゼンを用いた脂肪族カルボン酸の脱炭酸-臭素化反応の開発2018

    • Author(s)
      渡辺 歩実、宮本 和範、内山 真伸
    • Organizer
      日本プロセス化学会 2018 サマーシンポジウム
    • Related Report
      2018 Research-status Report
  • [Presentation] 三価の超原子価臭素および塩素化合物の合成、構造とその反応2018

    • Author(s)
      宮本 和範
    • Organizer
      ハロゲン利用ミニシンポジウム
    • Related Report
      2018 Research-status Report
    • Invited
  • [Presentation] Facile synthesis of (Diacetoxyiodo)arene using sodium hypochlorite2018

    • Author(s)
      Kazunori Miyamoto, Ayumi Watanabe, Tomohide Okada, Tomotake Asawa, Masanobu Uchiyama
    • Organizer
      6th International Conference on Hypervalent Iodine Chemistry 2018
    • Related Report
      2018 Research-status Report
    • Int'l Joint Research
  • [Presentation] 次亜塩素酸ナトリウム 5 水和物を用いるジアセトキシヨードアレーンの 効率的合成法の開発2018

    • Author(s)
      宮本 和範、渡辺 歩実、岡田 倫英、浅輪 智丈、内山 真伸
    • Organizer
      日本プロセス化学会 2018 サマーシンポジウム
    • Related Report
      2018 Research-status Report
  • [Presentation] ジアリール塩素(III)化合物:実用的合成法の開拓、構造とその合成化学的応用2018

    • Author(s)
      中島 美涼、宮本 和範、内山 真伸
    • Organizer
      第 44 回反応と合成の進歩シンポジウム
    • Related Report
      2018 Research-status Report
  • [Presentation] 立体障害に強い脱炭酸-臭素化反応の開発2018

    • Author(s)
      渡辺 歩実, 宮本 和範, 内山 真伸
    • Organizer
      第 44 回反応と合成の進歩シンポジウム
    • Related Report
      2018 Research-status Report
  • [Presentation] フッ素化カルバゾールを利用した青色の熱活性型遅延蛍光材料の合成と性質2018

    • Author(s)
      三浦 悠月, 白﨑 良尚, 村中 厚哉, 宮本 和範, 内山 真伸
    • Organizer
      第 8 回 CSJ 化学フェスタ 2018
    • Related Report
      2018 Research-status Report
  • [Presentation] カルボランアニオンを基盤とした新規弱配位性アニオン種の合成とその性能評価2018

    • Author(s)
      渡部 衛、北沢 裕、宮本 和範、内山 真伸
    • Organizer
      第 8 回 CSJ 化学フェスタ 2018
    • Related Report
      2018 Research-status Report
  • [Presentation] 新たな蛍光分子の創製を指向したアルキニルアミドのアルキニルホウ素化反応2018

    • Author(s)
      野上 摩利菜、森本 賢介、平野 圭一、谷岡 卓、宮本 和範、村中 厚哉、内山 真
    • Organizer
      第 29 回基礎有機化学討論会
    • Related Report
      2018 Research-status Report
  • [Patent(Industrial Property Rights)] 次亜塩素酸塩を用いた超原子価ヨウ素化合物の製造方法2019

    • Inventor(s)
      宮本和範、内山真伸、岡田倫英、浅輪智丈、外山高志
    • Industrial Property Rights Holder
      宮本和範、内山真伸、岡田倫英、浅輪智丈、外山高志
    • Industrial Property Rights Type
      特許
    • Filing Date
      2019
    • Acquisition Date
      2020
    • Related Report
      2020 Annual Research Report

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Published: 2018-07-25   Modified: 2022-01-27  

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