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Inert Bond Cleavage Reaction Mediated by External Physical-Chemical Stimuli

Research Project

Project/Area Number 18K06544
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Review Section Basic Section 47010:Pharmaceutical chemistry and drug development sciences-related
Research InstitutionThe University of Tokyo

Principal Investigator

WANG Chao  東京大学, 大学院薬学系研究科(薬学部), 助教 (90610436)

Project Period (FY) 2018-04-01 – 2021-03-31
Project Status Completed (Fiscal Year 2020)
Budget Amount *help
¥4,420,000 (Direct Cost: ¥3,400,000、Indirect Cost: ¥1,020,000)
Fiscal Year 2020: ¥1,170,000 (Direct Cost: ¥900,000、Indirect Cost: ¥270,000)
Fiscal Year 2019: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Fiscal Year 2018: ¥1,820,000 (Direct Cost: ¥1,400,000、Indirect Cost: ¥420,000)
Keywords不活性結合切断反応 / 天然資源分子 / 重合反応 / ラジカル反応 / 光化学反応 / 機能性分子創製 / 14 族元素化学 / 合成終盤的誘導体化 / タンパク質の標識 / DNA コード化ライブラリー / π共役ポリマー / 重縮合反応 / アリールエーテル / 電子移動反応 / 天然資源 / 不活性結合切断 / 誘導体化反応
Outline of Final Research Achievements

In this project, we have established several new protocols for efficient cleavages and transformations of inert C-O/C-N bonds under mild conditions, including 1) transition-metal-catalyzed cross-coupling polycondensation via C-O or C-N bond cleavage, 2) direct and diverse functionalization of arylammonium C-N bond via SNAr process, and 3) stereoselective syntheses of alkenes via photo-induced C(sp3)-N bond cleavage. We also developed the first protocol for photo-catalytic decarboxylation of sila- and germa-carboxylic acids leading to efficient generation of corresponding silyl and germyl radicals.

Academic Significance and Societal Importance of the Research Achievements

環境調和型循環社会の実現を鑑みると、天然資源・人工資源の効率的な変換・利用手法は、極めて挑戦的かつ実現すべき課題です。 C-O/C-N 結合は、天然物・医薬品・機能性材料において最も重要な構造単位の一つです。温和な条件下で、高効率・高選択的にこれらの結合を変換する反応は、資源の利用、物質創製や機能創生などの領域に大きく貢献できると考えられます。本研究では、新たな C-O/C-N 結合切断反応の実現と機能性分子創製への応用に取り組み、大きく発展させることを目標とします。天然資源を活用する合成化学の新展開を通して、医薬科学・物質科学において高いレベルの基礎研究・応用研究の達成を期待します。

Report

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

    (25 results)

All 2020 2019 2018 2017 Other

All Journal Article (15 results) (of which Int'l Joint Research: 8 results,  Peer Reviewed: 13 results,  Open Access: 6 results) Presentation (6 results) (of which Int'l Joint Research: 1 results,  Invited: 2 results) Remarks (4 results)

  • [Journal Article] Sila‐ and Germacarboxylic Acids: Precursors for the Corresponding Silyl and Germyl Radicals2020

    • Author(s)
      Xu Ning‐Xin、Li Bi‐Xiao、Wang Chao、Uchiyama Masanobu
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 59 Issue: 26 Pages: 10639-10644

    • DOI

      10.1002/anie.202003070

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Photo-Induced C(sp3)-N Bond Cleavage Leading to Stereoselective Syntheses of Alkenes2019

    • Author(s)
      Ze-Kun Yang, Ning-Xin Xu, Chao Wang, and Masanobu Uchiyama
    • Journal Title

      Chem. Eur. J.

      Volume: 25 Issue: 21 Pages: 5433-5439

    • DOI

      10.1002/chem.201900886

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] Non-transition Metal-Mediated Diverse Aryl-Heteroatom Bond Formation of Arylammonium Salts2019

    • Author(s)
      Dong-Yu Wang, Xin Wen, Chaodong Xiong, Jian-Nan Zhao, Chun-Yong Ding, Qian Meng, Hu Zhou, Chao Wang, Masanobu Uchiyama, Xiao-Jie Lu, and Ao Zhang
    • Journal Title

      iScience

      Volume: 15 Pages: 307-315

    • DOI

      10.1016/j.isci.2019.04.038

    • Related Report
      2019 Research-status Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Organocopper cross-coupling reaction for C-C Bond formation on highly sterically hindered structures2019

    • Author(s)
      Miku Oi, Ryo Takita, Junichiro Kanazawa, Atsuya Muranaka, Chao Wang, and Masanobu Uchiyama
    • Journal Title

      Chem. Sci.

      Volume: 10 Issue: 24 Pages: 6107-6112

    • DOI

      10.1039/c9sc00891h

    • Related Report
      2019 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Quadruple Borylation of Terminal Alkynes2019

    • Author(s)
      Daiki Yukimori, Yuki Nagashima, Chao Wang, Atsuya Muranaka, and Masanobu Uchiyama
    • Journal Title

      J. Am. Chem. Soc.

      Volume: 141 Issue: 25 Pages: 9819-9822

    • DOI

      10.1021/jacs.9b04665

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] 理論計算による生合成経路の探索2019

    • Author(s)
      佐藤玄、王超、内山真伸
    • Journal Title

      Farumashia

      Volume: 55 Issue: 7 Pages: 684-688

    • DOI

      10.14894/faruawpsj.55.7_684

    • NAID

      130007671600

    • ISSN
      0014-8601, 2189-7026
    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] 日本人科学者が先導した輝かしい化学の記録:クロスカップリング反応の生誕と発展の歴史(第1回/全2回)2019

    • Author(s)
      王超、内山真伸
    • Journal Title

      現代科学

      Volume: 557 Pages: 64-69

    • Related Report
      2019 Research-status Report
  • [Journal Article] 日本人科学者が先導した輝かしい化学の記録:クロスカップリング反応の生誕と発展の歴史(第2回/全2回)2019

    • Author(s)
      王超、内山真伸
    • Journal Title

      現代科学

      Volume: 558 Pages: 47-53

    • Related Report
      2019 Research-status Report
  • [Journal Article] Cross-coupling polycondensation via C-O or C-N bond cleavage2018

    • Author(s)
      Ze-Kun Yang, Ning-Xin Xu, Ryo Takita, Atsuya Muranaka, Chao Wang, Masanobu Uchiyama
    • Journal Title

      Nature Commun.

      Volume: 9 Issue: 1 Pages: 1587-1587

    • DOI

      10.1038/s41467-018-03928-z

    • Related Report
      2018 Research-status Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] From Anilines to Aryl Ethers: A Facile, Efficient, and Versatile Synthetic Method Employing Mild Conditions2018

    • Author(s)
      Wang Dong-Yu、Yang Ze-Kun、Wang Chao、Zhang Ao、Uchiyama Masanobu
    • Journal Title

      Angew. Chem. Int. Ed.

      Volume: 57 Issue: 14 Pages: 3641-3635

    • DOI

      10.1002/anie.201712618

    • Related Report
      2018 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] In Situ Generation of Silylzinc by Si-B Bond Activation Enabling Silylzincation and Silaboration of Terminal Alkynes2018

    • Author(s)
      Yuki Nagashima, Daiki Yukimori, Chao Wang, Masanobu Uchiyama
    • Journal Title

      Angew. Chem. Int. Ed. 2018, 57, 8053-8057

      Volume: 57 Issue: 27 Pages: 8053-8057

    • DOI

      10.1002/anie.201802887

    • Related Report
      2018 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Direct synthesis of aryl-annulated [c]carbazoles by gold(I)-catalysed cascade reaction of azide-diynes and arenes2018

    • Author(s)
      Yuiki Kawada, Shunsuke Ohmura, Misaki Kobayashi, Wataru Nojo, Masaki Kondo, Yuka Matsuda, Junpei Matsuoka, Shinsuke Inuki, Shinya Oishi, Chao Wang, Tatsuo Saito, Masanobu Uchiyama, Takanori Suzuki, Hiroaki Ohno
    • Journal Title

      Chem. Sci.

      Volume: 9 Issue: 44 Pages: 8416-8416

    • DOI

      10.1039/c8sc03525c

    • Related Report
      2018 Research-status Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Theoretical Study of Sesterfisherol Biosynthesis: Computational Prediction of Key Amino Acid Residue in Terpene Synthase2018

    • Author(s)
      Sato Hajime、Narita Koji、Minami Atsushi、Yamazaki Mami、Wang Chao、Suemune Hironori、Nagano Shingo、Tomita Takeo、Oikawa Hideaki、Uchiyama Masanobu
    • Journal Title

      Scientific Reports

      Volume: 8 Issue: 1 Pages: 2473-2473

    • DOI

      10.1038/s41598-018-20916-x

    • Related Report
      2018 Research-status Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Computational Study on a Puzzle in the Biosynthetic Pathway of Anthocyanin: Why is an Enzymatic Oxidation/ Reduction Process Required for a Simple Tautomerization?2018

    • Author(s)
      Hajime Sato, Chao Wang, Mami Yamazaki, Kazuki Saito, Masanobu Uchiyama
    • Journal Title

      PLoS ONE

      Volume: 13 Issue: 6 Pages: e0198944-e0198944

    • DOI

      10.1371/journal.pone.0198944

    • Related Report
      2018 Research-status Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Mechanistic Study on Aryl-Exchange Reaction of Diaryl-λ3-iodane with Aryl Iodide2017

    • Author(s)
      Masumoto Yui、Miyamoto Kazunori、Iuchi Takuto、Ochiai Masahito、Hirano Keiichi、Saito Tatsuo、Wang Chao、Uchiyama Masanobu
    • Journal Title

      J. Org. Chem.

      Volume: 83 Issue: 1 Pages: 289-295

    • DOI

      10.1021/acs.joc.7b02701

    • Related Report
      2018 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Presentation] 可視光下での脱炭酸反応を駆動力とするシリルラジカルの発生法の開発2020

    • Author(s)
      李 碧霄、徐 寧馨、王 超、内山 真伸
    • Organizer
      日本薬学会第 140 年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] Cross-Coupling via Ammonium or Pyridinium C-N Bond Cleavage2019

    • Author(s)
      Chao Wang, and Masanobu Uchiyama
    • Organizer
      27th International Society of Heterocyclic Chemistry Congress (ISHC-27)
    • Related Report
      2019 Research-status Report
    • Int'l Joint Research
  • [Presentation] C-O/C-N 結合切断を経由する共重合反応の開発2019

    • Author(s)
      楊沢コン、徐寧馨、村中厚哉、王超、内山真伸
    • Organizer
      第68回高分子討論会
    • Related Report
      2019 Research-status Report
  • [Presentation] 実験と理論の協奏で切り拓く高度分子変換反応の開発2018

    • Author(s)
      王 超
    • Organizer
      日本薬学会 第 138 年会
    • Related Report
      2018 Research-status Report
    • Invited
  • [Presentation] 実験と理論の協奏による新しい分子変換反応の開発2018

    • Author(s)
      王 超
    • Organizer
      3.第 6 回 BRIGHT Symposium (Bridging the RIsing Generations by Hybrid research in Tokushima)
    • Related Report
      2018 Research-status Report
    • Invited
  • [Presentation] アンモニウム C-N 結合切断型分子変換法の開発2018

    • Author(s)
      王 超、楊 沢コン、内山 真伸
    • Organizer
      第 65 回 有機金属化学討論会
    • Related Report
      2018 Research-status Report
  • [Remarks] 基于可見光促進的脱炭酸反応形成硅基自由基的新方法(中国語)

    • URL

      https://www.x-mol.com/news/451831

    • Related Report
      2020 Annual Research Report
  • [Remarks] 形成硅基自由基的新方法及其応用(中国語)

    • URL

      https://www.chembeango.com/zixun/49348

    • Related Report
      2020 Annual Research Report
  • [Remarks] Young Career Focus: Dr. Chao Wang(英語)

    • URL

      https://www.thieme.de/en/thieme-chemistry/synform-interview-with-chao-wang-159565.htm

    • Related Report
      2020 Annual Research Report
  • [Remarks] 不活性な C-O/C-N 結合を切断しながら高分子合成を行う新反応を開発

    • URL

      http://www.f.u-tokyo.ac.jp/topics.html?page=3&key=1524548576

    • Related Report
      2018 Research-status Report

URL: 

Published: 2018-04-23   Modified: 2022-01-27  

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