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新触媒活性種創製に基づくアミドの触媒的水素化の開拓

Publicly Offered Research

Project AreaMolecule Activation Directed toward Straightforward Synthesis
Project/Area Number 23105518
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 InstitutionNagoya University

Principal Investigator

斎藤 進  名古屋大学, 理学(系)研究科(研究院), 准教授 (90273268)

Project Period (FY) 2011-04-01 – 2013-03-31
Project Status Completed (Fiscal Year 2012)
Budget Amount *help
¥7,020,000 (Direct Cost: ¥5,400,000、Indirect Cost: ¥1,620,000)
Fiscal Year 2012: ¥3,510,000 (Direct Cost: ¥2,700,000、Indirect Cost: ¥810,000)
Fiscal Year 2011: ¥3,510,000 (Direct Cost: ¥2,700,000、Indirect Cost: ¥810,000)
Keywords水素化 / 不活性アミド / アミン / アルコール / ルテニウム錯体 / 分子触媒反応 / 新触媒活性種 / 環境負荷低減 / 遷移金属触媒 / 分子性の触媒表面
Outline of Annual Research Achievements

アミドは,ナイロン,ケブラーなどアミド系高分子,およびアクリルアミド,カプロラクタムなど高分子合成用のモノマーとしても工業的に大量生産可能である.タンパク質やオリゴペプチドとして自然界にも豊富に存在する.しかしながらアミド基はカルボニル基のなかで最も不活性であり,その水素化は速度論的にも熱力学的にも難しいとされてきた.アミドの水素化を実現する配位子には2つの特徴が求められる.第一にかさ高さ,第二に強い結合力である.これら二つの特徴を満たす配位子として(P,N)型二座配位子を選択した.我々は今回,そのような配位子をもつ新しい触媒前駆体Ru錯体を3種類開発した.なかでもRu錯体Cl2Ru(Cy2PCH2Py)2を触媒前駆体として用いることで,一般的な「不活性」アミドの選択的水素化に成功した.本手法は高い基質一般性を示し,1級アミド,2級アミド,3級アミドに有効である.鎖状のより不活性なアミドのみらなず,環状アミドにも適用可能である.反応機構を調べるなかで,触媒誘導段階でCl2Ru(Cy2PCH2Py)2の配位子のピリジン部位が完全に水素化されピペリジンになることも示された.すなわち配位子であるCy2PCH2PyがCyPCH2(piperidine)になったものが実際の触媒活性種に関わっていることを突き止めた.その結果,触媒誘導段階にのみ高温,高H2圧が必要で,実際のアミドの水素化でははより低温・低PH2(120 °C, 2 MPa)で十分であることを発見した.水銀テストによってRuナノパーティクルの触媒としての作用もほぼ無視できるため,H-Ru-N-H構造の構築に基づく「新触媒活性種」の二官能性機構を支持する有力な 情報を得たといえる.

Research Progress Status

24年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

24年度が最終年度であるため、記入しない。

Report

(2 results)
  • 2012 Annual Research Report
  • 2011 Annual Research Report
  • Research Products

    (43 results)

All 2013 2012 2011 Other

All Journal Article (11 results) (of which Peer Reviewed: 11 results) Presentation (17 results) (of which Invited: 6 results) Book (3 results) Remarks (6 results) Patent(Industrial Property Rights) (6 results)

  • [Journal Article] Reaction of an "Invisible" Frustrated N/B Lewis Pair with Dihydrogen2013

    • Author(s)
      Sina Schwendemann, Shunsuke Oishi, Susumu Saito, Roland Froehlich, Gerald Kehr, Gerhard Erker
    • Journal Title

      Chem. Asian J.

      Volume: 8 Issue: 1 Pages: 212-217

    • DOI

      10.1002/asia.201200776

    • Related Report
      2012 Annual Research Report
    • Peer Reviewed
  • [Journal Article] The Dual Role of Ruthenium and Alkali Base Catalysts in Enabling a Conceptually New shortcut to N-Unsubstituted Pyrroles via Unmasked α-Amino Aldehydes2013

    • Author(s)
      Kazuki Iida, Takashi Miura, Junki Ando, Susumu Saito
    • Journal Title

      Org. Lett.

      Volume: 15 Issue: 7 Pages: 1436-1439

    • DOI

      10.1021/ol4001262

    • Related Report
      2012 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Catalytic hydrogenation of unactivated amides enabled by hydrogenation of catalyst precursor2013

    • Author(s)
      三浦隆志、Ingmar E. HELD、大石俊輔、鳴戸真之、斎藤進
    • Journal Title

      Tetrahedron Letters

      Volume: 54 Issue: 21 Pages: 2674-2678

    • DOI

      10.1016/j.tetlet.2013.03.047

    • Related Report
      2012 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Acetals of N,N-Dimethylformamides: Ambiphilic Behavior in Converting Carbon Dioxide to Dialkyl Carbonates2013

    • Author(s)
      Yuki Takada, Aki Matsuoka, Ya Du, Hiroshi Naka, Susumu Saito
    • Journal Title

      Chem. Lett.

      Volume: 42 Issue: 2 Pages: 146-147

    • DOI

      10.1246/cl.2013.146

    • NAID

      130004426857

    • Related Report
      2012 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Redox-selective Generation of Aldehydes and H2 from Alcohols under Visible Light2013

    • Author(s)
      Zijun Liu, Joaquim Caner, Akihiko Kudo, Hiroshi Naka, Susumu Saito
    • Journal Title

      Chem. Eur. J.

      Volume: 19 Issue: 29 Pages: 9452-9456

    • DOI

      10.1002/chem.201301347

    • Related Report
      2012 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Double Molecular Recognition with Aminoorganoboron Complexes : Selective Alcoholysis of β-Dicarbonyl Derivatives2012

    • Author(s)
      Shunsuke Oishi, Susumu Saito
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 18(未定) Issue: 22 Pages: 5395-5399

    • DOI

      10.1002/anie.201200304

    • Related Report
      2012 Annual Research Report 2011 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Aldol Condensation of Carboxamide Using TAPC-based Catalysis2012

    • Author(s)
      Siong Wan Foo, Shun Oishi, Susumu Saito
    • Journal Title

      Tetrahedron Lett.

      Volume: 53 Issue: 40 Pages: 5445-5448

    • DOI

      10.1016/j.tetlet.2012.07.129

    • Related Report
      2012 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Catalytic Hydrogenation of Unactivated Amides Using Molecular Catalyst Surface Derived from Ruthenium Complex2012

    • Author(s)
      Takashi Miura, Ingmar E. Held, Shunsuke Oishi, Susumu Saito
    • Journal Title

      Catalysts and Catalysis

      Volume: 54 Pages: 455-459

    • NAID

      10031134309

    • Related Report
      2012 Annual Research Report
    • Peer Reviewed
  • [Journal Article] One-Pot Nitrile Aldoliztion/Hydration Operation Giving β-Hydroxy Carboxamides2011

    • Author(s)
      Goto, A.; Naka, H.; Noyori, R.; Saito, S.
    • Journal Title

      Chem.Asian J.

      Volume: 6 Pages: 1740-1743

    • Related Report
      2011 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Cu^I/H_2/NaOH-Catalyzed Cross Coupling of Two Different Alcohols for Carbon-Carbon Bond Formation : "Borrowing Hydrogen"?2011

    • Author(s)
      Miura, T.; Kose, O.; Li, F.; Sun, K.; Saito, S.
    • Journal Title

      Chem.Eur.J.

      Volume: 17 Issue: 40 Pages: 11146-11151

    • DOI

      10.1002/chem.201101752

    • Related Report
      2011 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Selective N-Alkylation of Amines with Alcohols by Using Non-Metal-Based Acid-Base Cooperative Catalysis2011

    • Author(s)
      Ya Du, Shunsuke Oishi, Susumu Saito
    • Journal Title

      Chemistry-A European Journal

      Volume: 17 Issue: 44 Pages: 12262-12267

    • DOI

      10.1002/chem.201102446

    • Related Report
      2011 Annual Research Report
    • Peer Reviewed
  • [Presentation] Catalytic Hydrogenation of Unactivated Amides2013

    • Author(s)
      Saito, S.
    • Organizer
      The 2nd Campus Asia Symposium on Frontiers of Chemistry and Materials
    • Place of Presentation
      Nanjing University, China
    • Year and Date
      2013-03-11
    • Related Report
      2012 Annual Research Report
    • Invited
  • [Presentation] Catalytic Hydrogenation of Unactivated Amides2012

    • Author(s)
      Saito, S.
    • Organizer
      1st KAUST- Symposium on Functional Molecules and Materials
    • Place of Presentation
      KAUST, Jeddah, Saudi Arabia
    • Year and Date
      2012-12-16
    • Related Report
      2012 Annual Research Report
    • Invited
  • [Presentation] Catalytic Hydrogenation of Unactivated Amides2012

    • Author(s)
      Saito, S.
    • Organizer
      17th Malaysian Chemical Congress (17MCC)
    • Place of Presentation
      Putra World Trade Centre, Kuala Lumpur, Malaysia
    • Year and Date
      2012-10-15
    • Related Report
      2012 Annual Research Report
    • Invited
  • [Presentation] Catalytic Transformation of Amides2012

    • Author(s)
      Saito, S.
    • Organizer
      The 13th Joint IRTG Symposium for Nagoya-Muenster University
    • Place of Presentation
      Muenster University, Germany
    • Year and Date
      2012-05-07
    • Related Report
      2012 Annual Research Report
    • Invited
  • [Presentation] Hydrogenicsに基づく炭素資源利用-不活性分子の活性化から医薬品の合成まで-2012

    • Author(s)
      斎藤進
    • Organizer
      CPhI Japan 2012
    • Place of Presentation
      東京ビッグサイト、東京(招待講演)
    • Year and Date
      2012-03-21
    • Related Report
      2011 Annual Research Report
  • [Presentation] Catalytic Alcoholysis of Amides2012

    • Author(s)
      Saito, S.
    • Organizer
      The First Nagoya Symposium on Green Synthesis & Catalysis (NSGSC-1)
    • Place of Presentation
      Nagoya University, Nagoya, Japan(招待講演)
    • Year and Date
      2012-03-13
    • Related Report
      2011 Annual Research Report
  • [Presentation] 脱石油化学に挑む:次世代触媒化学の創成を目指して2012

    • Author(s)
      斎藤進
    • Organizer
      平成24年度日本理化学協会東海ブロック研究会第18回研究発表大会
    • Place of Presentation
      愛知県教育会館,名古屋
    • Related Report
      2012 Annual Research Report
    • Invited
  • [Presentation] 化学で挑む21世紀の重要課題2012

    • Author(s)
      斎藤進
    • Organizer
      高等研究院初年次教育講義シリーズ「学問の面白さを知る」
    • Place of Presentation
      名古屋大学,名古屋
    • Related Report
      2012 Annual Research Report
    • Invited
  • [Presentation] 均一系触媒と不均一系触媒のインターフェース構築を目指して:アミドの触媒的水素化2012

    • Author(s)
      斎藤進
    • Organizer
      新学術領域研究「分子活性化」第2回公開シンポジウム
    • Place of Presentation
      京都大学桂キャンパス船井講堂、京都(招待講演)
    • Related Report
      2011 Annual Research Report
  • [Presentation] Toward the Construction of an Interface between Homogeneous and Heterogeneous Catalysis2012

    • Author(s)
      Saito, S.; Miura, T.; Oishi, S.
    • Organizer
      The CRC International Symposium on Green & Sustainable Catalysis : from Theoretical and Fundamental Aspects to Catalyst Design
    • Place of Presentation
      Hokkaido University, Sapporo, Japan(招待講演)
    • Related Report
      2011 Annual Research Report
  • [Presentation] ハイドロジェニクスに基づく炭素資源利用-アルコールの形成と反応の新展開2011

    • Author(s)
      斎藤進
    • Organizer
      第2回統合物質科学シンポジウム
    • Place of Presentation
      名古屋大学、名古屋(招待講演)
    • Year and Date
      2011-11-11
    • Related Report
      2011 Annual Research Report
  • [Presentation] 分子の左と右:野依教授の足跡と化学で挑む21世紀の重要課題2011

    • Author(s)
      斎藤進
    • Organizer
      名古屋大学高等研究院第1回アカデミーサロン
    • Place of Presentation
      名古屋大学、名古屋(招待講演)
    • Year and Date
      2011-08-01
    • Related Report
      2011 Annual Research Report
  • [Presentation] 新触媒活性種創製に基づくアミドの触媒的水素化2011

    • Author(s)
      斎藤進
    • Organizer
      新学術領域研究第1回全体会議
    • Place of Presentation
      大阪大学中之島センター、大阪(招待講演)
    • Related Report
      2011 Annual Research Report
  • [Presentation] Control of diversity in hydrogen transfer for drug synthesis : atom economical and rapid approach to Aricept^【○!R】 and Lipitor^【○!R】2011

    • Author(s)
      Saito, S.
    • Organizer
      The 2^<nd> International Symposium on Process Chemistry (ISPC211)
    • Place of Presentation
      Kyoto International Conference Center, Kyoto, Japan(招待講演)
    • Related Report
      2011 Annual Research Report
  • [Presentation] Control of Diversity in Hydrogen Atom Transfer for Organic Synthesis : New Aspects in Metal Alkoxide Catalysts2011

    • Author(s)
      Saito, S.
    • Organizer
      Satellite Meeting in The 14^<th> Asian Chemical Congress (ACC)
    • Place of Presentation
      Siem Reap, Cambodia(招待講演)
    • Related Report
      2011 Annual Research Report
  • [Presentation] Control of Diversity in Hydrogen Atom Transfer in Molecular Catalysis : "Borrowing Hydrogen" or Not?2011

    • Author(s)
      Saito, S.
    • Organizer
      The 5^<th> Asian Network of Metal Chemistry in The 14^<th> Asian Chemical Congress (ACC)
    • Place of Presentation
      Bangkok, Thailand(招待講演)
    • Related Report
      2011 Annual Research Report
  • [Presentation] Hydrogenics : Principle and Applications2011

    • Author(s)
      Saito, S.
    • Organizer
      The 11^<th> Tateshina Conference on Organic Chemistry
    • Place of Presentation
      Tateshina Forum, Chino (Nagano), Japan(招待ポスター発表)
    • Related Report
      2011 Annual Research Report
  • [Book] 二酸化炭素の直接利用技術最前線2013

    • Author(s)
      中寛史,斎藤進
    • Total Pages
      11
    • Publisher
      NTS出版
    • Related Report
      2012 Annual Research Report
  • [Book] Science of Synthesis, Houben-Weyl Methods of Molecular Transformation ; Al-H-Update2011

    • Author(s)
      H.Naka, S.Saito
    • Publisher
      Thieme : Stuttgart
    • Related Report
      2011 Annual Research Report
  • [Book] Science of Synthesis, Houben-Weyl Methods of Molecular Transformation : Al-X-Update2011

    • Author(s)
      H.Naka, S.Saito
    • Publisher
      Thieme : Stuttgart
    • Related Report
      2011 Annual Research Report
  • [Remarks] 論文:ピロール合成

    • URL

      http://noy.chem.nagoya-u.ac.jp/noy_j/Top/entori/2013/3/8_lun_wenpiroru_he_cheng.html

    • Related Report
      2012 Annual Research Report
  • [Remarks] 論文:不活性アミドの水素化

    • URL

      http://noy.chem.nagoya-u.ac.jp/noy_j/Top/entori/2012/12/1_lun_wen_bu_huo_xingamidono_shui_su_hua.html

    • Related Report
      2012 Annual Research Report
  • [Remarks] 論文:見えない酸-塩基で水素を活性化

    • URL

      http://noy.chem.nagoya-u.ac.jp/noy_j/Top/entori/2012/10/31_lun_wen_jianenai_suanyan_jide_shui_suwo_huo_xing_hua.html

    • Related Report
      2012 Annual Research Report
  • [Remarks] 論文:アミドの直接変換

    • URL

      http://noy.chem.nagoya-u.ac.jp/noy_j/Top/entori/2012/8/4_lun_wenamidono_zhi_jie_bian_huan.html

    • Related Report
      2012 Annual Research Report
  • [Remarks] 論文:均一系触媒

    • URL

      http://noy.chem.nagoya-u.ac.jp/noy_j/Top/entori/2012/4/16_lun_wen_jun_yi_xi_chu_mei.html

    • Related Report
      2012 Annual Research Report
  • [Remarks]

    • URL

      http://www.organic-chemistry.org/Highlights/2011/31October.shtm

    • Related Report
      2011 Annual Research Report
  • [Patent(Industrial Property Rights)] 配位子、その配位子を含む金属錯体、及びその金属錯体を 用いた反応2013

    • Inventor(s)
      斎藤進、野依良治、三浦隆志、鳴戸真之、飯田和希、他5名
    • Industrial Property Rights Holder
      国立大学法人 名古屋大学
    • Industrial Property Rights Type
      特許
    • Industrial Property Number
      2013-042385
    • Filing Date
      2013-03-04
    • Related Report
      2012 Annual Research Report
  • [Patent(Industrial Property Rights)] 環状ウレタンの製造方法2013

    • Inventor(s)
      斎藤進、野依良治、中寛史、Siong Wan Foo
    • Industrial Property Rights Holder
      国立大学法人 名古屋大学
    • Industrial Property Rights Type
      特許
    • Industrial Property Number
      2013-065083
    • Filing Date
      2013-03-26
    • Related Report
      2012 Annual Research Report
  • [Patent(Industrial Property Rights)] カルボニル化合物の製造方法2012

    • Inventor(s)
      斎藤進、野依良治、中寛史、工藤昭彦、他2名
    • Industrial Property Rights Holder
      国立大学法人 名古屋大学
    • Industrial Property Rights Type
      特許
    • Industrial Property Number
      2012-181888
    • Filing Date
      2012-08-20
    • Related Report
      2012 Annual Research Report
  • [Patent(Industrial Property Rights)] ルテニウム錯体、水素移動反応用触媒及び水素移動反応物の製造方法2012

    • Inventor(s)
      斎藤進、野依良治、三浦隆志、Ingmar Held, 鈴木めぐみ、飯田和希、高田雄貴
    • Industrial Property Rights Holder
      国立大学法人名古屋大学
    • Filing Date
      2012-01-23
    • Related Report
      2011 Annual Research Report
  • [Patent(Industrial Property Rights)] 環状ウレタンの製造方法2012

    • Inventor(s)
      斎藤進、野依良治、中寛史、山崎祐輔、Foo, Siong Wan
    • Industrial Property Rights Holder
      国立大学法人名古屋大学
    • Industrial Property Number
      2012-028845
    • Filing Date
      2012-02-13
    • Related Report
      2011 Annual Research Report
  • [Patent(Industrial Property Rights)] 環状ウレタンの製造方法2012

    • Inventor(s)
      斎藤進、野依良治、中寛史、山崎祐輔、高田雄貴
    • Industrial Property Rights Holder
      国立大学法人名古屋大学
    • Industrial Property Number
      2012-070113
    • Filing Date
      2012-03-26
    • Related Report
      2011 Annual Research Report

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Published: 2011-04-06   Modified: 2018-03-28  

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