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Development of novel heterocumulenes for the formations of multi-substituted heterocyclic compounds

Research Project

Project/Area Number 18K14204
Research Category

Grant-in-Aid for Early-Career Scientists

Allocation TypeMulti-year Fund
Review Section Basic Section 33010:Structural organic chemistry and physical organic chemistry-related
Research InstitutionRikkyo University

Principal Investigator

SUGAMATA Koh  立教大学, 理学部, 助教 (80646886)

Project Period (FY) 2018-04-01 – 2020-03-31
Project Status Completed (Fiscal Year 2019)
Budget Amount *help
¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000)
Fiscal Year 2019: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000)
Fiscal Year 2018: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000)
Keywordsヘテロアレン / 高周期16族元素 / 単結晶X線構造解析 / カルベン錯体 / 高周期典型元素 / ヘテロクムレン / カルコゲン / X線結晶構造解析 / 1,3-双極子反応 / 有機典型元素化合物 / カルコゲノフェン
Outline of Final Research Achievements

Recently, we have successfully synthesized and isolated of the first sulfur- and selenium-centered allene-type bis(methylene)sulfane and bis(methylene)selane as stable compounds. In the present study, the reactions of these bis(methylene)chalcogenanes with HCl and halogenation reagents such as SO2Cl2 and Br2 afforded the corresponding 1,3-adducts quantitatively. Unexpectedly, the reactions of chalcogen-centered heteroallenes with AuCl(SMe2) gave the stable (thio) and (seleno)(silyl)carbene gold(I) complexes.

Academic Significance and Societal Importance of the Research Achievements

高周期典型元素を中心とするヘテロアレン類は、炭素のみからなるアレン類とは大きく異なるユニークな性質を有する。しかしながら、空気中において不安定である化合物がほとんどであり、その合成・単離例は少なく反応性の調査もほとんど行われていない。本研究課題では、最近合成・単離に成功した高周期16族元素である硫黄やセレンを中心とするヘテロアレン類を用い、その反応性を調査したところ1,3-付加型の反応性を起こすことを明らかとした。この結果を鑑み、求双極子剤との1,3-付加反応が効率的に進行すれば、これまでにない含高周期16族元素複素環合成が可能となり、新規色素や電子材料へと応用が期待される。

Report

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

    (12 results)

All 2020 2019 2018 Other

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

  • [Journal Article] A stable bis(methylene)-λ4-selane with a >C=Se=C< bond containing Se(iv)2019

    • Author(s)
      Koh Sugamata, Yukiko Urao, Mao Minoura
    • Journal Title

      Chemical Communications

      Volume: 55 Issue: 57 Pages: 8254-8257

    • DOI

      10.1039/c9cc04121d

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis and Structure of a Stable Bis(methylene)-λ4-sulfane2018

    • Author(s)
      Sugamata Koh、Hashizume Daisuke、Suzuki Yuko、Sasamori Takahiro、Ishii Shigeru
    • Journal Title

      Chemistry - A European Journal

      Volume: 24 Issue: 27 Pages: 6922-6926

    • DOI

      10.1002/chem.201800828

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Presentation] (カルコゲノ)(シリル)カルベン金錯体(I)の合成と構造2020

    • Author(s)
      浦尾有紀子, 菅又功, 箕浦真生
    • Organizer
      日本化学会第100春季年会
    • Related Report
      2019 Annual Research Report
  • [Presentation] Stable Bis(methylene)-λ4-selane; The Type of >C=Se=C< with Se(IV)”2019

    • Author(s)
      Urao, Y.; Sugamata, K.; Minoura, M.
    • Organizer
      14th International Conference on the Chemistry of Selenium and Tellurium (ICCST-14), Sardinia, Italy, June 3-7 2019.
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Synthesis, structures, and properties of stable bis(methylene)-λ4-chalcogenanes2019

    • Author(s)
      Sugamata, K.; Urao, Y. Minoura, M.
    • Organizer
      13th International Conference on Heteroatom Chemistry (ICHAC 2019), Prague, Czech Republic, June 30-July 05 2019.
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research
  • [Presentation] 硫黄・セレンを含む累積多重結合化合物の合成と構造2019

    • Author(s)
      浦尾有紀子, 菅又功, 箕浦真生
    • Organizer
      第30回基礎有機化学討論会
    • Related Report
      2019 Annual Research Report
  • [Presentation] セレンを中心とするヘテロアレンBis(methylene)-λ4-selaneの合成と性質2019

    • Author(s)
      浦尾有紀子, 菅又功, 箕浦真生
    • Organizer
      第5回日本セレン研究
    • Related Report
      2019 Annual Research Report
  • [Presentation] ビス(メチレン)-λ4-セランの反応性2019

    • Author(s)
      浦尾有紀子, 菅又功, 箕浦真生
    • Organizer
      第46回有機典型元素化学討論会
    • Related Report
      2019 Annual Research Report
  • [Presentation] Synthesis and Structure of a Stable Bis(methylene)-l4-sulfane2018

    • Author(s)
      Koh Sugamata, Daisuke Hashizume, Yuko Suzuki, Takahiro Sasamori, Shigeru Ishii, Yukiko Urao, Mao Minoura
    • Organizer
      28th International Symposium on the Organic Chemistry of Sulfur
    • Related Report
      2018 Research-status Report
    • Int'l Joint Research
  • [Presentation] セレンを中心とする新規ヘテロアレンの合成2018

    • Author(s)
      浦尾有紀子、菅又 功、箕浦真生
    • Organizer
      第45回有機典型元素化学討論会
    • Related Report
      2018 Research-status Report
  • [Presentation] 高周期16族元素を中心とする新規ヘテロアレンの合成と性質2018

    • Author(s)
      浦尾有紀子、菅又 功、箕浦真生
    • Organizer
      日本化学会第99春季年会
    • Related Report
      2018 Research-status Report
  • [Remarks] 立教大学理学部未来プロジェクト研究室

    • URL

      https://sites.google.com/rikkyo.ac.jp/miraiproject/home

    • Related Report
      2019 Annual Research Report

URL: 

Published: 2018-04-23   Modified: 2021-02-19  

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