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Development of flexibly designable organic reducing agents and their application(Fostering Joint International Research)

Research Project

Project/Area Number 15KK0186
Research Category

Fund for the Promotion of Joint International Research (Fostering Joint International Research)

Allocation TypeMulti-year Fund
Research Field Synthetic chemistry
Research InstitutionOsaka University

Principal Investigator

Tsurugi Hayato  大阪大学, 基礎工学研究科, 准教授 (60432514)

Project Period (FY) 2016 – 2019
Project Status Completed (Fiscal Year 2019)
Budget Amount *help
¥15,600,000 (Direct Cost: ¥12,000,000、Indirect Cost: ¥3,600,000)
Keywords有機ケイ素還元剤 / 低原子価錯体 / 還元的切断 / メタセシス反応 / 前周期遷移金属 / 環化付加反応 / アゾ化合物 / メタロリガンド / 還元的活性化 / イミド配位子 / ピロール合成 / 表面有機金属化学 / 還元反応 / 固体触媒 / 有機分子還元剤
Outline of Final Research Achievements

"Single-site heterogeneous catalyst" is a new type catalyst having advantages of both homogeneous and heterogeneous catalysts. Catalyst activation of such the heterogeneous catalyst is generally required high reaction temperature. By using an organosilicon reducing agent applicable to reduction of various metal complexes, activation of such the heterogeneous catalysts is accomplished under the mild reaction conditions, resulted in lowering the thermal energy required for the use of heterogeneous catalysts. Low catalyst activation temperature enabled us to apply the heterogeneous catalyst system for low-temperature metathesis reactions using functionalized alkenes. In addition, low-valent species generated by the organosilicon reducing agent was effective for the cleavage of a N=N bond of azobenzene and catalytic pyrrole formation with internal alkynes via metal-catalyzed cycloaddition reaction.

Academic Significance and Societal Importance of the Research Achievements

不均一系触媒の活性化、特に単一の活性中心が表面に存在する「シングルサイト性不均一系触媒」に対して、金属錯体の還元反応に利用可能な有機ケイ素還元剤を用いることにより、温和な条件で触媒活性化が可能であるとする、不均一系触媒の利用時のエネルギーコストの大幅な削減につながる研究成果を得た。有機反応剤により不均一系触媒の表面状態を劇的に変えることが可能である本還元剤の役割は、不均一系触媒の改質や失活後の再活性化につながる基盤的知見となる点で、学術的にも意義深い成果である。

Report

(5 results)
  • 2019 Annual Research Report   Final Research Report ( PDF )
  • 2018 Research-status Report
  • 2017 Research-status Report
  • 2016 Research-status Report
  • Research Products

    (13 results)

All 2020 2019 2018 2016 Other

All Int'l Joint Research (2 results) Journal Article (5 results) (of which Int'l Joint Research: 5 results,  Peer Reviewed: 5 results) Presentation (3 results) Remarks (3 results)

  • [Int'l Joint Research] University of Minnesota(米国)2018

    • Year and Date
      2018-09-25
    • Related Report
      2019 Annual Research Report
  • [Int'l Joint Research] ETH Zurich(スイス)2016

    • Related Report
      2019 Annual Research Report
  • [Journal Article] Reactivity of terminal imido complexes of group 4?6 metals: Stoichiometric and catalytic reactions involving cycloaddition with unsaturated organic molecules2020

    • Author(s)
      Kawakita Kento、Parker Bernard F.、Kakiuchi Yuya、Tsurugi Hayato、Mashima Kazushi、Arnold John、Tonks Ian A.
    • Journal Title

      Coordination Chemistry Reviews

      Volume: 407 Pages: 213118-213118

    • DOI

      10.1016/j.ccr.2019.213118

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Synthesis of Pyridylimido Complexes of Tantalum and Niobium by Reductive Cleavage of the N?N Bond of 2,2′-Azopyridine: Precursors for Early?Late Heterobimetallic Complexes2019

    • Author(s)
      Kawakita Kento、Kakiuchi Yuya、Beaumier Evan P.、Tonks Ian A.、Tsurugi Hayato、Mashima Kazushi
    • Journal Title

      Inorganic Chemistry

      Volume: 58 Issue: 22 Pages: 15155-15165

    • DOI

      10.1021/acs.inorgchem.9b02043

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Bis(imido)vanadium(V)-Catalyzed [2+2+1] Coupling of Alkynes and Azobenzenes Giving Multisubstituted Pyrroles2019

    • Author(s)
      Kento Kawakita, Evan P. Beaumier, Yuya Kakiuchi, Hayato Tsurugi, Ian A. Tonks, Kazushi Mashima
    • Journal Title

      Journal of the American Chemical Society

      Volume: 141 Issue: 10 Pages: 4194-4198

    • DOI

      10.1021/jacs.8b13390

    • Related Report
      2018 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Activation of O2 by Organosilicon Reagents Yields Quantitative Amounts of H2O2 or (Me3Si)2O2 for Efficient O‐Transfer Reactions2018

    • Author(s)
      Keishi Yamamoto, Shinji Tanaka, Hiromu Hosoya, Hayato Tsurugi, Kazushi Mashima, Christophe Coperet
    • Journal Title

      Helvetica Chimica Acta

      Volume: 101 Issue: 12

    • DOI

      10.1002/hlca.201800156

    • Related Report
      2018 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Silica-Supported Isolated Molybdenum Di-oxo Species: Formation and Activation with Organosilicon Agent for Olefin Metathesis2018

    • Author(s)
      Keishi Yamamoto, Ka Wing Chan, Victor Mougel, Haruki Nagae, Hayato Tsurugi, Olga V. Safonova, Kazushi Mashima, and Christophe Coperet
    • Journal Title

      Chem. Commun.

      Volume: 54 Issue: 32 Pages: 3989-3992

    • DOI

      10.1039/c8cc01876f

    • Related Report
      2017 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Presentation] 2,2’-アゾピリジンの窒素-窒素二重結合の還元的切断を経たタンタル及びニオブのピリジルイミド錯体の合成とロジウム錯体との複核錯体形成2020

    • Author(s)
      垣内 勇哉・川北 健人・Evan Beaumier・秋山 拓弥・Ian A. Tonks・劒 隼人・真島 和志
    • Organizer
      日本化学会第100春季年会
    • Related Report
      2019 Annual Research Report
  • [Presentation] バナジウム錯体を触媒としたアルキンとアゾベンゼンの [2+2+1]-環化付加反応による多置換ピロール合成反応2019

    • Author(s)
      垣内 勇哉・川北 健人・BEAUMIER Evan・TONKS Ian・劒 隼人・真島 和志
    • Organizer
      日本化学会第99春季年会
    • Related Report
      2018 Research-status Report
  • [Presentation] Mechanistic Study on Vanadium-catalyzed [2+2+1]-cycloaddition of Alkynes and Azobenzenes2019

    • Author(s)
      KAWAKITA, Kento; KAKIUCHI, Yuya; BEAUMIER, Evan; TONKS, Ian; TSURUGI, Hayato; MASHIMA, Kazushi
    • Organizer
      日本化学会第99春季年会
    • Related Report
      2018 Research-status Report
  • [Remarks] 大阪大学大学院基礎工学研究科真島研究室HP

    • URL

      http://www.chem.es.osaka-u.ac.jp/organomet/

    • Related Report
      2019 Annual Research Report
  • [Remarks] 真島研究室HP

    • URL

      http://www.chem.es.osaka-u.ac.jp/organomet/

    • Related Report
      2018 Research-status Report 2017 Research-status Report
  • [Remarks] Coperet研究室HP

    • URL

      http://www.coperetgroup.ethz.ch/

    • Related Report
      2017 Research-status Report

URL: 

Published: 2016-10-04   Modified: 2023-01-30  

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