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らせん不斉を有する錯体触媒の開発と不斉酸化反応への応用

Publicly Offered Research

Project AreaCoordination Asymmetry: Design of Asymmetric Coordination Sphere and Anisotropic Assembly for the Creation of Functional Molecules
Project/Area Number 19H04560
Research Category

Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)

Allocation TypeSingle-year Grants
Review Section Science and Engineering
Research InstitutionUniversity of Tsukuba

Principal Investigator

小島 隆彦  筑波大学, 数理物質系, 教授 (20264012)

Project Period (FY) 2019-04-01 – 2021-03-31
Project Status Completed (Fiscal Year 2020)
Budget Amount *help
¥4,810,000 (Direct Cost: ¥3,700,000、Indirect Cost: ¥1,110,000)
Fiscal Year 2020: ¥2,470,000 (Direct Cost: ¥1,900,000、Indirect Cost: ¥570,000)
Fiscal Year 2019: ¥2,340,000 (Direct Cost: ¥1,800,000、Indirect Cost: ¥540,000)
Keywordsらせん不斉 / ルテニウム錯体 / 不斉酸化反応
Outline of Research at the Start

不斉中心を持たないアキラルな多座ピリジルアミン配位子をルテニウムに配位させ、配位子に導入したかさ高い芳香族置換基の立体障害とキレート配位によって、ルテニウム中心にらせん不斉を発生させる。そのらせん不斉ルテニウム錯体を触媒とし、ルテニウム(IV)-オキソ錯体を酸化活性種として発生させ、その反応性を精査する。それらの知見に基づいて、前例のない不斉酸化触媒反応系の開発を目指す。

Outline of Annual Research Achievements

本研究では、トリス (2-ピリジルメチル)アミン(TPA)の2つのピリジン環の6位に、アミド結合を介して不斉な官能基を導入したピリジルアミン配位子、及びアミド結合を介して嵩高い芳香族置換基を導入したピリジルアミン配位子を合成し、ルテニウム錯体に結合させることで、金属近傍への不斉点の導入、及びらせん不斉を誘起させたメタロヘリケートの形成による、新規な不斉酸化触媒系の構築を試みた。本年度の成果は、以下の通りである。
新たに、TPA配位子にアミド結合を介して1-ナフチル基を3位に有するベンゼン環を有する、N,N-Bis(6-(3’-(naphth-1”-yl)benzamide)-pyrid-2-yl-methyl)-N-(2-pyridylmethyl)amine ((3-NP-CONH)2-TPA)を合成し、そのRu(II)錯体の合成とキャラクタリゼーションを行った。生成したRu(II)-クロロ錯体の光学分割を、キラルな対イオンとのイオン対形成、キラルなカラムを用いたHPLCによる分離などによって試みたが、光学分割には至らなかった。次に、トリフルオロエタノール(TFE):水(1:1)混合溶媒中で、(3-NP-CONH)2-TPAを配位子とするRu(II)錯体を(NH4)2[Ce(NO3)6] (CAN)によって電子移動酸化し、Ru(III)-OCH2CF3錯体が生成することを明らかにした。そのRu(III)種を酸化活性種として、プロトン共役電子移動を経由するベンジルアルコール類の酸化反応が進行することを見いだした。なお、さまざまな基質や反応条件を検討したが、残念ながら不斉酸化反応の開発には至らなかった。

Research Progress Status

令和2年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

令和2年度が最終年度であるため、記入しない。

Report

(1 results)
  • 2020 Annual Research Report
  • Research Products

    (23 results)

All 2021 2020 Other

All Journal Article (14 results) (of which Peer Reviewed: 12 results) Presentation (7 results) (of which Int'l Joint Research: 2 results,  Invited: 2 results) Book (1 results) Remarks (1 results)

  • [Journal Article] Long-Range Order in Supramolecular π Assemblies in Discrete Multidecker Naphthalenediimides2021

    • Author(s)
      Sudhir Kumar Keshri, Tomoya Ishizuka, Takahiko Kojima, Yoshitaka Matsushita, Masayuki Takeuchia、Takeuchi Masayuki
    • Journal Title

      Journal of the American Chemical Society

      Volume: 143 Issue: 8 Pages: 3238-3244

    • DOI

      10.1021/jacs.0c13389

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Efficient Near-Infrared Light-Driven Hydrogen Evolution Catalyzed by a Saddle-Distorted Porphyrin as a Photocatalyst2020

    • Author(s)
      H. Kotani, T. Miyazaki, E. Aoki, H. Sakai, T. Hasobe, T. Kojima
    • Journal Title

      ACS. Appl. Eenergy Mater.

      Volume: 3 Issue: 4 Pages: 3193-3197

    • DOI

      10.1021/acsaem.0c00206

    • NAID

      120007170585

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Development of functionality of metal complexes based on proton-coupled electron transfer2020

    • Author(s)
      Kojima Takahiko
    • Journal Title

      Dalton Transactions

      Volume: 49 Issue: 22 Pages: 7284-7293

    • DOI

      10.1039/d0dt00898b

    • NAID

      130007808055

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] A Mechanistic Dichotomy in Two‐Electron Reduction of Dioxygen Catalyzed by N,N’‐Dimethylated Porphyrin Isomers2020

    • Author(s)
      Wataru Suzuki, Hiroaki Kotani, Tomoya Ishizuka, Takahiko Kojima
    • Journal Title

      Chemistry-A European Journal

      Volume: 26 Issue: 46 Pages: 10480-10486

    • DOI

      10.1002/chem.202000942

    • NAID

      120007170584

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Discrete π Stack of a Tweezer‐Shaped Naphthalenediimide-Anthracene Conjugate2020

    • Author(s)
      Sudhir Kumar Keshri, Waka Nakanishi, Atsuro Takai, Tomoya Ishizuka, Takahiko Kojima, Masayuki Takeuchi
    • Journal Title

      Chemistry-A European Journal

      Volume: 26 Issue: 58 Pages: 13288-13294

    • DOI

      10.1002/chem.202002477

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Cooperative Effects of Heterodinuclear IrIII-MII Complexes on Catalytic H2 Evolution from Formic Acid Dehydrogenation in Water2020

    • Author(s)
      Dachao Hong, Yoshihiro Shimoyama, Yuji Ohgomori, Ryoichi Kanega, Hiroaki Kotani, Tomoya Ishizuka, Yoshihiro Kon, Yuichiro Himeda, Takahiko Kojima
    • Journal Title

      Inorganic Chemistry

      Volume: 59 Issue: 17 Pages: 11976-11985

    • DOI

      10.1021/acs.inorgchem.0c00812

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Selective Catalytic 2e--Oxidation of Organic Substrates by an FeII Complex Having an N-Heterocyclic Carbene Ligand in Water2020

    • Author(s)
      Hiroto Fujisaki, Tomoya Ishizuka, Yoshihiro Shimoyama, Hiroaki Kotani, Yoshihito Shiota, Kazunari Yoshizawa, Takahiko Kojima
    • Journal Title

      Chemical Communications

      Volume: 56 Issue: 68 Pages: 9783-9786

    • DOI

      10.1039/d0cc03289a

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Redox Properties of a Bipyrimidine-Bridged Dinuclear Ruthenium(II) Complex2020

    • Author(s)
      Tomoya Ishizuka, Masaki Itogawa, Hinatsu Shimomura, Yoshihito Shiota, Hiroaki Kotani, Kazunari Yoshizawa, Takahiko Kojima
    • Journal Title

      Inorganic Chemistry Communications

      Volume: 120 Pages: 108150-108150

    • DOI

      10.1016/j.inoche.2020.108150

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Study on Proton-Coupled Electron Transfer in Transition Metal Complexes2020

    • Author(s)
      Kojima Takahiko
    • Journal Title

      Bulletin of the Chemical Society of Japan

      Volume: 93 Issue: 12 Pages: 1571-1582

    • DOI

      10.1246/bcsj.20200213

    • NAID

      130007955886

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Mechanistic Insight into Concerted Proton-Electron Transfer of a Ru(IV)-Oxo Complex: A Possible Oxidative Asynchronicity2020

    • Author(s)
      Hiroaki Kotani, Hinatsu Shimomura, Kei Ikeda, Tomoya Ishizuka, Yoshihito Shiota, Kazunari Yoshizawa, Takahiko Kojima
    • Journal Title

      Journal of the American Chemical Society

      Volume: 142 Issue: 40 Pages: 16982-16989

    • DOI

      10.1021/jacs.0c05738

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Selective Convergence to Atropisomers of a Porphyrin Derivative Having Bulky Substituents at the Periphery2020

    • Author(s)
      Tomoya Ishizuka, Shogo Tanaka, Sayaka Uchida, Lianyu Wei, Takahiko Kojimako
    • Journal Title

      The Journal of Organic Chemistry

      Volume: 85 Issue: 20 Pages: 12856-12869

    • DOI

      10.1021/acs.joc.0c01876

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Photocatalytic Hydrogen Evolution Using a Ru(II)-Bound Heteroaromatic Ligand as a Reactive Site2020

    • Author(s)
      Takuya Sawaki, Tomoya Ishizuka, Nanase Namura, Dachao Hong, Mayuko Miyanishi, Yoshihito Shiota, Hiroaki Kotani, Kazunari Yoshizawa, Jieun Jung, Shunichi Fukuzumi, Takahiko Kojima
    • Journal Title

      Dalton Transactions

      Volume: 49 Issue: 47 Pages: 17230-17242

    • DOI

      10.1039/d0dt03546g

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] ルテニウム錯体触媒による基質酸化反応機構2020

    • Author(s)
      小島隆彦
    • Journal Title

      触媒

      Volume: 62 Pages: 400-405

    • NAID

      40022578122

    • Related Report
      2020 Annual Research Report
  • [Journal Article] 金属錯体におけるプロトン共役電子移動に基づく機能発現2020

    • Author(s)
      小島隆彦
    • Journal Title

      Organometallic News

      Volume: 2 Pages: 34-39

    • Related Report
      2020 Annual Research Report
  • [Presentation] Mechanistic Insights into Proton-Coupled Electron Transfer in Ruthenium Complexes2021

    • Author(s)
      Takahiko Kojima,
    • Organizer
      2020 Dalian University of Technology-Overseas Partner Universities Series Online Exchange Conference
    • Related Report
      2020 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Application of Saddle-Distorted Porphyrins to Dioxygen Reduction2020

    • Author(s)
      Takahiko Kojima
    • Organizer
      237th ECS Meeting
    • Related Report
      2020 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] サドル型ポルフィリンを光増感剤とした近赤外光駆動型光触媒的水素発生2020

    • Author(s)
      宮崎卓也、青木絵美、小谷弘明、酒井隼人、羽曾部卓、小島隆彦
    • Organizer
      2020年web光化学討論会
    • Related Report
      2020 Annual Research Report
  • [Presentation] Cooperative Effects of Hetero-Dinuclear Ir<sup>III</sup>-M<sup>II</sup> Complexes on Catalytic H<sub>2</sub> Evolution from Formic Acid Dehydrogenation in Water2020

    • Author(s)
      Dachao Hong, Yoshihiro Shimoyama, Yuji Ohgomori, Ryoichi Kanega, Hiroaki Kotani, Tomoya Ishizuka, Yoshihiro Kon, Yuichiro Himeda, Takahiko Kojima
    • Organizer
      錯体化学会第70回討論会
    • Related Report
      2020 Annual Research Report
  • [Presentation] Fe<sup>II</sup>-NHC錯体を触媒とする水中における有機基質の高選択的二電子酸化反応2020

    • Author(s)
      藤崎寛人、石塚智也、下山祥弘、小谷弘明、塩田淑仁、吉澤一成、小島隆彦
    • Organizer
      第53回酸化反応討論会
    • Related Report
      2020 Annual Research Report
  • [Presentation] ルテニウム(IV)-オキソ錯体のプロトン共役電子移動とその反応機構解明2020

    • Author(s)
      小谷弘明、下村日夏、池田京、石塚智也、塩田淑仁、吉澤一成、小島隆彦
    • Organizer
      第53回酸化反応討論会
    • Related Report
      2020 Annual Research Report
  • [Presentation] 水中での有機化合物の触媒的酸化反応2020

    • Author(s)
      小島隆彦
    • Organizer
      第2回筑波大学産学連携シンポジウム ―人と社会の未来に向けてー
    • Related Report
      2020 Annual Research Report
  • [Book] 脱石油に向けたCO2資源化技術、第17章:ニッケル錯体触媒によるCO2光還元2020

    • Author(s)
      湯川英明(監修)、小島隆彦
    • Total Pages
      375
    • Publisher
      シーエムシー出版
    • ISBN
      9784781315102
    • Related Report
      2020 Annual Research Report
  • [Remarks] 筑波大学数理物質系化学域 小島研究室

    • URL

      http://www.chem.tsukuba.ac.jp/kojima/Site/Site/Home.html

    • Related Report
      2020 Annual Research Report

URL: 

Published: 2019-04-18   Modified: 2021-12-27  

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