• Search Research Projects
  • Search Researchers
  • How to Use
  1. Back to previous page

Activation of H-H, Si-H, and C-H bonds on the transition metal-main metal bond: Fundamental studies and applications to catalysis

Research Project

Project/Area Number 18K19082
Research Category

Grant-in-Aid for Challenging Research (Exploratory)

Allocation TypeMulti-year Fund
Review Section Medium-sized Section 33:Organic chemistry and related fields
Research InstitutionKyushu University

Principal Investigator

Nagashima Hideo  九州大学, グリーンテクノロジー研究教育センター, 特任教授 (50159076)

Co-Investigator(Kenkyū-buntansha) 田原 淳士  九州大学, 先導物質化学研究所, 助教 (50713145)
Project Period (FY) 2018-06-29 – 2020-03-31
Project Status Completed (Fiscal Year 2019)
Budget Amount *help
¥6,240,000 (Direct Cost: ¥4,800,000、Indirect Cost: ¥1,440,000)
Fiscal Year 2019: ¥2,470,000 (Direct Cost: ¥1,900,000、Indirect Cost: ¥570,000)
Fiscal Year 2018: ¥3,770,000 (Direct Cost: ¥2,900,000、Indirect Cost: ¥870,000)
Keywords非古典的結合活性化 / 遷移金属―典型金属結合 / ジシラメタラサイクル / ヒドロシラン / 均一系触媒反応 / 還元反応 / カルボニル化合物 / 遷移金属 / 典型金属 / 基質活性化 / 触媒反応 / 有機金属錯体
Outline of Final Research Achievements

The present experimental and theoretical research realized a paradigm shift on the mechanisms of catalytic reactions, in which unconventional bond activation of reactants occurring on a transition metal-main group metal bond is more common and useful for developments of highly efficient catalytic reactions. The outstanding results are exemplified by highly efficient hydrosilylation of carbonyl compounds by ruthenium-disilametallacycle catalysts and highly efficient conversion of tertiary amides to enamines with excellent functional group compatibility. The latter was suggested to be achieved by the silicon-hydrogen bond activation on the iridium-silicon bond. The reaction applied synthesis of new donor-acceptor compounds showing unique photo-luminescence properties.

Academic Significance and Societal Importance of the Research Achievements

極めて高い触媒効率、反応選択性での触媒的有機・高分子合成反応は、低環境負荷での医農薬、機能性材料開発の鍵とされている。その実現には、新しい触媒、触媒反応設計概念の確立が求められる。本研究では、従来信じられてきた「反応基質の結合活性化は遷移金属上で起こる」触媒反応から、「結合活性化は遷移金属―典型金属上で起こる」触媒反応へのパラダイムシフトを理論的、実験的に実証し、その応用例として、イリジウム―ケイ素上で起こることが示唆されている、ケイ素―水素結合活性化がドナー・アクセプター型π共役エナミンを基盤とした新規蛍光材料合成に有用であることを示した。

Report

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

    (21 results)

All 2020 2019 2018 Other

All Int'l Joint Research (1 results) Journal Article (6 results) (of which Int'l Joint Research: 1 results,  Peer Reviewed: 6 results) Presentation (11 results) (of which Int'l Joint Research: 3 results,  Invited: 6 results) Book (1 results) Remarks (1 results) Patent(Industrial Property Rights) (1 results) (of which Overseas: 1 results)

  • [Int'l Joint Research] CNRS, LCC)(フランス)

    • Related Report
      2018 Research-status Report
  • [Journal Article] Recent topics of iridium-catalyzed hydrosilylation of tertiary amides to silylhemiaminals2020

    • Author(s)
      A. Tahara, H. Nagashima
    • Journal Title

      Tetrahedron Letters

      Volume: 61 Issue: 4 Pages: 151423-151431

    • DOI

      10.1016/j.tetlet.2019.151423

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Theoretical Study on the Rhodium-Catalyzed Hydrosilylation of C=C and C=O Double Bonds with Tertiary Silane2019

    • Author(s)
      Zhao Liming、Nakatani Naoki、Sunada Yusuke、Nagashima Hideo、Hasegawa Jun-ya
    • Journal Title

      The Journal of Organic Chemistry

      Volume: 84 Issue: 13 Pages: 8552-8561

    • DOI

      10.1021/acs.joc.9b00959

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Donor?Acceptor π-Conjugated Enamines: Functional Group-Compatible Synthesis from Amides and Their Photoabsorption and Photoluminescence Properties2019

    • Author(s)
      Tahara Atsushi、Kitahara Ikumi、Sakata Daichi、Kuninobu Yoichiro、Nagashima Hideo
    • Journal Title

      The Journal of Organic Chemistry

      Volume: 84 Issue: 23 Pages: 15236-15254

    • DOI

      10.1021/acs.joc.9b02267

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] 原子移動ラジカル重合用鉄触媒設計法2019

    • Author(s)
      永島英夫
    • Journal Title

      触媒

      Volume: 61 Pages: 124-129

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Iridium-PPh3 Catalysts for Conversion of Amides to Enamines2019

    • Author(s)
      Une Yuta、Tahara Atsushi、Miyamoto Yasumitsu、Sunada Yusuke、Nagashima Hideo
    • Journal Title

      Organometallics

      Volume: 38 Issue: 4 Pages: 852-862

    • DOI

      10.1021/acs.organomet.8b00835

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Journal Article] Remarkably high catalyst efficiency of a disilaruthenacyclic complex for hydrosilane reduction of carbonyl compounds2018

    • Author(s)
      Tahara Atsushi、Sunada Yusuke、Takeshita Takashi、Inoue Ryoko、Nagashima Hideo
    • Journal Title

      Chemical Communications

      Volume: 54 Issue: 79 Pages: 11192-11195

    • DOI

      10.1039/c8cc04780d

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Presentation] Activation of H-H and H-Si bonds by transition metal-silicon linkage2020

    • Author(s)
      H. Nagashima
    • Organizer
      The 3rd IRCCS - The 2nd Reaction Infography Joint International Symposium
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] 制御されたラジカル重合用Fe(II)錯体触媒の設計,2020

    • Author(s)
      永島英夫
    • Organizer
      九州錯体化学懇談会第259回例会
    • Related Report
      2019 Annual Research Report
    • Invited
  • [Presentation] Ir-catalyzed Syntheses of Donor-;Acceptor pai-Conjugated Enamines and Their Photoluminescence Properties2020

    • Author(s)
      田原 淳士, 北原 いくみ, 坂田 大地, 國信 洋一郎, 永島 英夫
    • Organizer
      日本化学会 第 100 回 春季年会
    • Related Report
      2019 Annual Research Report
  • [Presentation] 金属ジアリール錯体とアルコールまたはカルボン酸との反応による新規鉄およびコバルト錯体の合成およびアルケンの触媒的ヒドロシリル化2020

    • Author(s)
      二宮 俊吾, 田原 淳士, 永島 英夫
    • Organizer
      日本化学会 第 100 回 春季年会
    • Related Report
      2019 Annual Research Report
  • [Presentation] Hydrosilane Reduction of Tertiary Amides: Controlling of the Product Selectivity by Transition Metal Catalysts2020

    • Author(s)
      立川 晴紀, 真川 敦嗣, 永島 英夫,
    • Organizer
      日本化学会 第 100 回 春季年会
    • Related Report
      2019 Annual Research Report
  • [Presentation] Environmentally Friendly Polymer Synthesis by Transition Metal Catalysts2019

    • Author(s)
      H. Nagashima
    • Organizer
      The International Polymer Conference of Thailand (PCT-9),
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] イリジウム触媒を用いたアミドの化学選択的ヒドロシラン還元による D-A 型 pai-共役エナミンの合成2019

    • Author(s)
      田原 淳士, 北原 いくみ, 坂田 大地, 國信 洋一郎, 永島 英夫
    • Organizer
      第23回ケイ素化学協会シンポジウム
    • Related Report
      2019 Annual Research Report
  • [Presentation] Ir-Catalyzed Chemoselective Hydrosilane Reduction of Carboxamides bearing Electron-Withdrawing Group Leading to the Formation of Donor-Acceptor-Type pai-Conjugated Enamines and Their Photochemical Properties2019

    • Author(s)
      田原 淳士, 北原 いくみ, 坂田 大地, 國信 洋一郎, 永島 英夫
    • Organizer
      第 66 回 有機金属化学討論会
    • Related Report
      2019 Annual Research Report
  • [Presentation] 4.Catalytic Hydrogenation Reactions by New Organometallic Catalysts2019

    • Author(s)
      Hideo Nagashima
    • Organizer
      PACCON 2019
    • Related Report
      2018 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] 遷移金属とケイ素の結合がもたらす効率的な触媒反応2018

    • Author(s)
      永島 英夫
    • Organizer
      第22回ケイ素科学シンポジウム
    • Related Report
      2018 Research-status Report
    • Invited
  • [Presentation] 3.Highly Efficient Iridium-catalyzed Reduction of Amides to Enamines with 1,1,3,3-Tetramethyldisiloxane (TMDS): Catalyst design, Mechanisms, and Applications2018

    • Author(s)
      Hideo Nagashima
    • Organizer
      The 18th Japan-Korea Joint Symposium on Organometallic and Coordination Chemistry
    • Related Report
      2018 Research-status Report
    • Invited
  • [Book] Organosilicon Chemistry: Novel Approach and Reactions2020

    • Author(s)
      Yusuke Sunada and Hideo Nagashima
    • Total Pages
      21
    • Publisher
      Wiley-VCH
    • ISBN
      9783527344536
    • Related Report
      2019 Annual Research Report
  • [Remarks] 研究室HP

    • URL

      http://nagashima-lab.cm.kyushu-u.ac.jp/

    • Related Report
      2018 Research-status Report
  • [Patent(Industrial Property Rights)] 有機光学材料2018

    • Inventor(s)
      國信洋一郎、金井
    • Industrial Property Rights Holder
      國信洋一郎、金井
    • Industrial Property Rights Type
      特許
    • Filing Date
      2018
    • Related Report
      2018 Research-status Report
    • Overseas

URL: 

Published: 2018-07-25   Modified: 2021-02-19  

Information User Guide FAQ News Terms of Use Attribution of KAKENHI

Powered by NII kakenhi