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Synthesis of azaphospholes from phosphaalkynes and their reactivities

Research Project

Project/Area Number 16K05767
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Research Field Synthetic chemistry
Research InstitutionThe University of Tokyo

Principal Investigator

NAKAJIMA Kazunari  東京大学, 大学院工学系研究科(工学部), 准教授 (10709471)

Project Period (FY) 2016-04-01 – 2019-03-31
Project Status Completed (Fiscal Year 2018)
Budget Amount *help
¥4,940,000 (Direct Cost: ¥3,800,000、Indirect Cost: ¥1,140,000)
Fiscal Year 2018: ¥780,000 (Direct Cost: ¥600,000、Indirect Cost: ¥180,000)
Fiscal Year 2017: ¥910,000 (Direct Cost: ¥700,000、Indirect Cost: ¥210,000)
Fiscal Year 2016: ¥3,250,000 (Direct Cost: ¥2,500,000、Indirect Cost: ¥750,000)
Keywords有機金属化学 / 錯体化学 / リン / ホスファアルキン / 環化付加 / ヘテロ環 / 銅触媒 / 環化付加反応 / 遷移金属触媒 / ホスホール
Outline of Final Research Achievements

Phosphorous-containing aromatic compounds are an attractive class of motifs in materials science and coordination chemistry. Hence, development of a new synthetic method is important. However, construction of phosphorous-containing pi-conjugated system is usually difficult and examples of conventional synthetic methods are limited.
Recently, our group found a transition metal-catalyzed synthetic methods of phosphabenzenes from phosphaalkynes, P-C triple bond compounds, based on the [2+2+2]-type cycloaddition reaction.
Based on the background, herein, I apply the synthetic method toward 1,3-azaphosphole, a five-membered aromatic compounds, and examined its reactivity.

Academic Significance and Societal Importance of the Research Achievements

含リン芳香族化合物は電子材料や遷移金属錯体の配位子として利用可能であるため、興味深い合成対称であるが、合成法が乏しく、そのためにその機能や反応性が十分に検討されていない。
今回、本研究代表者らは、そのような含リン芳香族化合物の中から、未だ合成例の限られている1,3-アザホスホールをターゲットとした。そして、銅触媒を用いたイソシアニドとホスファアルキンの[3+2]型の環化付加反応を開発した。この反応について、反応機構を明らかにするとともに、得られた1,3-アザホスホールをさらに誘導化することにも成功し、新たな反応性を見出すことができた。

Report

(4 results)
  • 2018 Annual Research Report   Final Research Report ( PDF )
  • 2017 Research-status Report
  • 2016 Research-status Report
  • Research Products

    (14 results)

All 2019 2018 2017 2016 Other

All Journal Article (3 results) (of which Peer Reviewed: 3 results,  Acknowledgement Compliant: 1 results) Presentation (9 results) (of which Int'l Joint Research: 1 results) Remarks (2 results)

  • [Journal Article] Copper-catalyzed [3+2] cycloaddition reactions of isocyanoacetates with phosphaalkynes to prepare 1,3-azaphospholes2019

    • Author(s)
      W. Liang, K. Nakajima*, K. Sakata*, Y. Nishibayashi*
    • Journal Title

      Angew. Chem., Int. Ed.

      Volume: 58 Issue: 4 Pages: 1168-1173

    • DOI

      10.1002/anie.201812779

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Hydroboration of Alkynes Catalyzed by Pyrrolide-Based PNP Pincer-Iron Complexes2017

    • Author(s)
      Kazunari Nakajima, Takeru Kato, Yoshiaki Nishibayashi
    • Journal Title

      Organic Letters

      Volume: 19 Issue: 16 Pages: 4323-4326

    • DOI

      10.1021/acs.orglett.7b01995

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] Iron-Catalyzed [2+2+2] Cycloaddition Reactions of Diynes with Oxyphosphaethynes to Construct 2-Phosphaphenol Derivatives2016

    • Author(s)
      K. Nakajima, W. Liang, Y. Nishibayashi
    • Journal Title

      Org. Lett.

      Volume: 18 Issue: 19 Pages: 5006-5009

    • DOI

      10.1021/acs.orglett.6b02462

    • Related Report
      2016 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Presentation] Synthesis of 1,2,4-Azadiphosphole Derivatives Based on Vanadium-Catalyzed [2+2+1] Cycloaddition Reactions of Phosphaalkynes with Azobenzenes2019

    • Author(s)
      Wenbin Liang, Kazunari Nakajima, Yoshiaki Nishibayashi
    • Organizer
      日本化学会第99春季年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] Synthesis of 1,3-Azaphospholes Based on Copper-Catalyzed [3+2] Cycloaddition Reactions of Phosphaalkynes2018

    • Author(s)
      Wenbin Liang, Kazunari Nakajima, Yoshiaki Nishibayashi
    • Organizer
      43rd International Conference on Coordination Chemistry
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research
  • [Presentation] ピロール骨格PNP型ピンサー配位子を持つ鉄錯体を触媒とする芳香環のC-Hホウ素化反応の開発2018

    • Author(s)
      加藤孟、中島一成、西林仁昭
    • Organizer
      日本化学会第98春季年会
    • Related Report
      2017 Research-status Report
  • [Presentation] Synthesis of Phosphorous-Heterocycles Based on Transition Metal-Catalyzed Cycloaddition Reactions of Phosphaalkynes2018

    • Author(s)
      Kazunari Nakajima, Wenbin Liang, Ken Sakata, Yoshiaki Nishibayashi
    • Organizer
      日本化学会第98春季年会
    • Related Report
      2017 Research-status Report
  • [Presentation] Synthesis of 1,3-Azaphosphole Derivatives Based on Copper-Catalyzed [3+2] Cycloaddition Reactions of Phosphaalkynes with Isocyanides2017

    • Author(s)
      Wenbin Liang, Kazunari Nakajima, Yoshiaki Nishibayashi
    • Organizer
      日本化学会第97春季年会
    • Place of Presentation
      慶應義塾大学日吉キャンパス(神奈川県横浜市)
    • Year and Date
      2017-03-16
    • Related Report
      2016 Research-status Report
  • [Presentation] Synthesis of 1,3-Azaphospholes Based on Copper-Catalyzed [3+2] Cycloaddition Reactions of Phosphaalkynes with Isocyanides2017

    • Author(s)
      Wenbin Liang, Kazunari Nakajima, Yoshiaki Nishibayashi
    • Organizer
      第64回有機金属化学討論会
    • Related Report
      2017 Research-status Report
  • [Presentation] ピロール型PNPピンサー配位子を持つ鉄錯体を触媒とするアルキンのヒドロホウ素化反応の開発2017

    • Author(s)
      加藤孟、中島一成、西林仁昭
    • Organizer
      錯体化学第67回討論会
    • Related Report
      2017 Research-status Report
  • [Presentation] Synthesis of 1,3-Azaphospholes Based on Copper-Catalyzed [3+2] Cycloaddition Reactions2017

    • Author(s)
      Liang Wenbin, Kazunari Nakajima, Ken Sakata, Yoshiaki Nishibayashi
    • Organizer
      第44回有機典型元素化学討論会
    • Related Report
      2017 Research-status Report
  • [Presentation] 鉄触媒を用いた[2+2+2]環化付加反応によるホスファフェノール誘導体の合成2016

    • Author(s)
      Wenbin Liang, 中島一成、西林仁昭
    • Organizer
      第43回有機典型元素化学討論会
    • Place of Presentation
      仙台市民会館(宮城県仙台市)
    • Year and Date
      2016-12-08
    • Related Report
      2016 Research-status Report
  • [Remarks] 西林研究室ウェブページの研究業績

    • URL

      http://park.itc.u-tokyo.ac.jp/nishiba/publications.html

    • Related Report
      2017 Research-status Report
  • [Remarks] 西林研究室ウェブページの研究業績

    • URL

      http://webpark1495.sakura.ne.jp/publications.html

    • Related Report
      2016 Research-status Report

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Published: 2016-04-21   Modified: 2020-03-30  

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