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Generalization and application of vinylidene rearrangement of disubstituted alkynes

Research Project

Project/Area Number 18K05154
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Review Section Basic Section 34010:Inorganic/coordination chemistry-related
Research InstitutionChuo University

Principal Investigator

ISHII Youichi  中央大学, 理工学部, 教授 (40193263)

Co-Investigator(Kenkyū-buntansha) 桑原 拓也  中央大学, 理工学部, 助教 (60768654)
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: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000)
Fiscal Year 2019: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Fiscal Year 2018: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Keywordsビニリデン転位 / ルテニウム / モリブデン / イリジウム / ヘテロ元素 / 結晶二色性 / ビニリデン / 逆転位 / ホスホリルアルキン / スルフェニルアルキン / ビニリデン錯体 / ヘテロ原子置換アルキン / 鉄 / スルホニルアルキン / 二置換アルキン / 15・16族元素
Outline of Final Research Achievements

This studty aimed at development of (1) novel metal complex systems that promote vinylidene rearrangement of carbon-disubstituted internal alkynes and (2) vinylidene rearrangement of heteroatom-substituted internal alkynes, especially those with group 15 and 16 substituents. Thus, we have discovered that [(C7H7)MoBr(dppe)] promotes vinylidene rearrangement of internal keto-alkynes in the presence of NaBArF4. On the other hand, P-, S-, and N-substituted internal alkynes such as alkynylphosphonates and alkynyl sulphides were found to be transformed into the vinylidene complexes at [CpRu(dppe)]+, [CpFe(dppe)]+, and [Cp*IrCl(PPh3)]+, and some of the complexes could be converted back to the alkyne on reactions with PPh3. In addition, some of the ruthenium vinylidene complexes derived from alkynylphosphonates and alkynyl sulfones exhibited crystallochromatic phenomena, and the origin of the dichromism was discussed on the basis of the TD-DFT calculations and X-ray diffraction studies.

Academic Significance and Societal Importance of the Research Achievements

アルキン錯体からビニリデン錯体を生成するビニリデン転位は、有機合成にも広く応用される重要な反応であるが、従来末端アルキンのみで実施可能とされてきた。我々は近年、炭素置換基を2つ持つ二置換アルキンでも、ビニリデン転位が可能であることを示しているが、まだ例は少ない。本研究では、モリブデンやイリジウムにも内部アルキンのビニリデン転位が可能な金属錯体系を拡張することに成功し、また従来ほとんど知見のなかった15・16族元素の置換基を持つ二置換アルキンのビニリデン転位も見出すことができた。これにより、ビニリデン転位が遷移金属錯体上において一般性の高い反応であることを実証できた。

Report

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

    (11 results)

All 2021 2020 2019 2018

All Journal Article (3 results) (of which Peer Reviewed: 3 results) Presentation (8 results) (of which Int'l Joint Research: 2 results)

  • [Journal Article] Direct Formation of Disubstituted Vinylidenes from Internal Alkynes at Group 8 Metal Complexes and its Application to Organic Synthesis2020

    • Author(s)
      武藤雄一郎・石井洋一・斎藤慎一
    • Journal Title

      Journal of Synthetic Organic Chemistry, Japan

      Volume: 78 Issue: 7 Pages: 691-702

    • DOI

      10.5059/yukigoseikyokaishi.78.691

    • NAID

      130007871497

    • ISSN
      0037-9980, 1883-6526
    • Year and Date
      2020-07-01
    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Ruthenium Vinylidene Complexes Generated by Selective 1,2-Migration of P- and S- Substituents: Synthesis, Structures, and Dichromism Arising from an Intermolecular CH…O Hydrogen Bond2020

    • Author(s)
      Takuya Kuwabara, Yutaka Aoki, Kousuke Sakajiri, Kazuki Deguchi, ShuheiTakamori, Ai Hamano, Keiko Takano, Hirohiko Houjou and Youichi Ishii
    • Journal Title

      Organometallics

      Volume: 39 Issue: 5 Pages: 711-718

    • DOI

      10.1021/acs.organomet.9b00856

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] Molybdenum-Mediated Vinylidene Rearrangement of Internal Acyalkynes and Sulfonylalkynes2019

    • Author(s)
      T. Kuwabara, K. Sakajiri, Y. Oyama, S. Kodama, Y. Ishii
    • Journal Title

      Organometallics

      Volume: 38 Issue: 7 Pages: 1560-1566

    • DOI

      10.1021/acs.organomet.9b00019

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Presentation] ヘテロ元素置換基を持つルテニウムビニリデン錯体の逆ビニリデン転位2021

    • Author(s)
      齋藤京花・岩本貴寛・桑原拓也・石井洋一
    • Organizer
      日本化学会第101春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] Ir錯体上での15,16族元素置換内部アルキンのビニリデン転位2020

    • Author(s)
      青木寛・高森修平・桑原拓也・石井洋一
    • Organizer
      錯体化学会第70回討論会
    • Related Report
      2020 Annual Research Report
  • [Presentation] 鉄錯体上でのスルホニルおよびチオアルキンのビニリデン転位と生成物のクロミズム挙動2020

    • Author(s)
      関口 雄平・青木 寛・桑原 拓也・石井 洋一
    • Organizer
      日本化学会第100春季年会
    • Related Report
      2019 Research-status Report
  • [Presentation] Ir錯体上での15,16族元素置換内部アルキンのビニリデン転位2020

    • Author(s)
      青木 寛・高森 修平・桑原 拓也・石井 洋一
    • Organizer
      日本化学会第100春季年会
    • Related Report
      2019 Research-status Report
  • [Presentation] 15, 16族元素置換基を持つRu二置換ビニリデン錯体のクロミズム挙動の解明2019

    • Author(s)
      青木寛・坂尻浩祐・出口和樹・桑原拓也・小玉晋太朗・鷹野景子・北條博彦・石井洋一
    • Organizer
      錯体化学会第69回討論会
    • Related Report
      2019 Research-status Report
  • [Presentation] 15・16族元素置換基を持つルテニウム二置換ビニリデン錯体の合成とそのクロミズム挙動2019

    • Author(s)
      坂尻浩祐・青木 寛・ 出口和樹・桑原拓也・北條博彦・石井洋一
    • Organizer
      日本化学会第99春季年会
    • Related Report
      2018 Research-status Report
  • [Presentation] Vinylidene Rearrangement of Internal Acyl- and Sulfonylalkynes in Molybdenum(0) Complexes2018

    • Author(s)
      K. Sakajiri, Y. Oyama, T. Kuwabara, S. Kodama, Y. Ishii
    • Organizer
      28th International Conference on Organometallic Chemistry
    • Related Report
      2018 Research-status Report
    • Int'l Joint Research
  • [Presentation] Vinylidene Rearrangement of Groups 15 and 16 Element Substituted Internal Alkynes2018

    • Author(s)
      S. Takamori, K. Sakajiri, K. Deguchi, S. Kodama, T. Kuwabara, Y. Ishii
    • Organizer
      28th International Conference on Organometallic Chemistry
    • Related Report
      2018 Research-status Report
    • Int'l Joint Research

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

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