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2011 Fiscal Year Final Research Report

Catalytic Asymmetric Hydrogenation of Ketones Using non-Phosphine-Based N4 Ligands

Research Project

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Project/Area Number 21350053
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Synthetic chemistry
Research InstitutionNagoya University

Principal Investigator

KITAMURA Masato  名古屋大学, 物質科学国際研究センター, 教授 (50169885)

Project Period (FY) 2009 – 2011
Keywords不斉合成 / 機構解明
Research Abstract

Homogeneous asymmetric hydrogenation of ketones using chiral diphosphine-Ru(II) complexes has been established as one of the most reliable strategies for the synthesis of optically active secondary alcohols since our Ru(OCOCH-3)-2(binap)/HCl combined catalyst made its debut in 1987. Having apparently started a trend with BINAP. Ru systems, a tremendous number of hydrogenation-active Ru complexes with trivalent phosphorus ligating atoms have been reported. The effectiveness has been examined and compared with the" privileged" BINAP system and its derivatives. In comparison, asymmetric hydrogenation using non-phosphine-based Ru complexes is still in the developmental stage. We have designed and synthesized Ph-BINAN-H-Py(3, 3'-Ph, Ph-N2, N2'-bis(pyridin-2-ylmethyl)-1, 1'-binaphthyl-2, 2'-diamine) which is characterized by a) inside sp^3N/outside sp^2N, b) donor-acceptor bifunctional ability, and c) cis-alpha-selective formation of octahedral metal complexes. The utility of ligands has been demonstrated in asymmetric hydrogenation of aromatic ketones in combination with a Ru-π-allyl precursor. The reaction quantitatively proceeds with the S/C ratio of over 10, 000 with up to 99 : 1 enantioselectivity. The success using non-phosphine ligand has made a new trail to asymmetric hydrogenation chemistry.

  • Research Products

    (34 results)

All 2012 2011 2010 2009

All Journal Article (15 results) (of which Peer Reviewed: 15 results) Presentation (16 results) Book (3 results)

  • [Journal Article] Asymmetric Dehydrative C-, N-, and O-Allylation Using Naph-diPIM-dioxoi-Pr-CpRu/p-TsOH Combined Catalyst2012

    • Author(s)
      K. Miyata, M. Kitamura
    • Journal Title

      Synthesis

      Volume: 44

    • DOI

      DOI:10.1055/s-0031-1290301

    • Peer Reviewed
  • [Journal Article] Reaction of Frustrated Lewis Pairs with Ketones and Esters2012

    • Author(s)
      B.-H. Xu, R. A. A. Yanez, H. Nakatsuka, M. Kitamura, R. Frohlich, G. Kehr, G. Erker
    • Journal Title

      Chem. Asian J.

    • DOI

      DOI:10.1002/asia.201100960

    • Peer Reviewed
  • [Journal Article] Double Arylation of Acetylenedicarboxylate with B(C_6F_5) 32012

    • Author(s)
      H. Nakatsuka, R. Frohlich, M. Kitamura, G. Kehr, G. Erker
    • Journal Title

      Eur. J. Inorg. Chem.

      Pages: 1163-1166

    • Peer Reviewed
  • [Journal Article] Enantioselective Synthesis of Pyrrolidine-, Piperidine-, and Azepane-Type N-Heterocycles withα-Alkenyl Substitution : The CpRu-Catalyzed Dehydrative Intramolecular N-Allylation Approach2012

    • Author(s)
      T. Seki, S. Tanaka, M. Kitamura
    • Journal Title

      Org. Lett

      Volume: 14 Pages: 608-611

    • Peer Reviewed
  • [Journal Article] Desymmetric Hydrogenation of a meso-Cyclic Acid Anhydride Toward Biotin Synthesis2011

    • Author(s)
      M. Yoshimura, K. Tsuda, H. Nakatsuka, T. Yamamura, M. Kitamura
    • Journal Title

      Tetrahedron

      Volume: 67 Pages: 10006-10010

    • Peer Reviewed
  • [Journal Article] A Chiral Bidentate sp^2-N Ligand, Naph-diPIM : Application to CpRu-Catalyzed Asymmetric Dehydrative C-, N-, and O-Allylation2011

    • Author(s)
      K. Miyata, H. Kutsuna, S. Kawakami, M. Kitamura
    • Journal Title

      Angew. Chem. Int. Ed

      Volume: 50 Pages: 4649-4653

    • Peer Reviewed
  • [Journal Article] Catalytic Dehydrative S-Allylation of Cysteine-Containing Peptides in Aqueous Media toward Lipopeptide Chemistry2011

    • Author(s)
      P. Jaisankar, S. Tanaka, M. Kitamura
    • Journal Title

      J. Org. Chem.

      Volume: 76 Pages: 1894-1897

    • Peer Reviewed
  • [Journal Article] Mechanistic Insight into NOYORI Asymmetric Hydrogenations2011

    • Author(s)
      M. Kitamura, H. Nakatsuka
    • Journal Title

      Chem. Commun

      Volume: 47 Pages: 842-846

    • Peer Reviewed
  • [Journal Article] Ruthenium(1+),(^5-2, 4-Cyclopentadien-1-yl)(^3-2-propen-1-yl)(2-quinolinecarboxyla to-N1, O2)-, Hexafluorophosphate(1?)(1 : 1)2010

    • Author(s)
      S. Tanaka, M. Kitamura
    • Journal Title

      E-eros

      Pages: 153

    • DOI

      DOI:10.1002/047084289X.rn01153

    • Peer Reviewed
  • [Journal Article] (9H-Fluoren-9-yl) methanesulfonyl(Fms): An Amino Protecting Group Complementary to Fmoc2010

    • Author(s)
      Y. Ishibashi, K. Miyata, M. Kitamura
    • Journal Title

      Eur. J. Org. Chem.

      Pages: 4201-4204

    • Peer Reviewed
  • [Journal Article] Synthesis of 3, 3'-Diaryl-substituted 2, 2'-diamino-1, 1'-binaphthyl(diAr-BINAN) and Its Derivatives2010

    • Author(s)
      M. Yoshimura, T. Muraoka, H. Nakatsuka, H. Huang, M. Kitamura
    • Journal Title

      J. Org. Chem.

      Volume: 75 Pages: 4315-4318

    • Peer Reviewed
  • [Journal Article] Highly Efficient Catalytic Dehydrative S-Allylation of Thiols and Thioic S-Acids2010

    • Author(s)
      S. Tanaka, P. K. Pradhan, Y. Maegawa, M. Kitamura
    • Journal Title

      Chem. Commun

      Volume: 46 Pages: 3996-3998

    • Peer Reviewed
  • [Journal Article] Asymmetric Dehydrative Cyclization ofω-Hydroxy Allyl Alcohols Catalyzed by Ruthenium Complexes2009

    • Author(s)
      S. Tanaka, T. Seki, M. Kitamura
    • Journal Title

      Angew. Chem. Int. Ed

      Volume: 48 Pages: 8948-8951

    • Peer Reviewed
  • [Journal Article] Solid-phase Synthesis of Protectedα-Amino Phosphonic Acid Oligomers2009

    • Author(s)
      Y. Ishibashi, M. Kitamura
    • Journal Title

      Chem. Commun

      Pages: 6985-6987

    • Peer Reviewed
  • [Journal Article] A Magnetically Separable Heterogeneous Deallylation Catalyst :[CpRu(η^3-C-3H-5)(2-pyridinecarboxylato)] PF-6 Complex Supported on a Ferromagnetic Microsize Particle Fe-3O-4@ SiO-22009

    • Author(s)
      T. Hirakawa, S. Tanaka, N. Usuki, H. Kanzaki, M. Kishimoto, M. Kitamura
    • Journal Title

      Eur. J. Org. Chem.

      Pages: 789-792

    • Peer Reviewed
  • [Presentation] Design and Synthesis of Chiral PicolinicAcid Derivatives and Their Application to CpRu2011

    • Author(s)
      M. Kitamura
    • Organizer
      International Symposium on Catalysisand Fine Chemicals 2011
    • Place of Presentation
      Nara
    • Year and Date
      2011-12-04
  • [Presentation] 脱水型不斉アリル化触媒の開発2011

    • Author(s)
      北村雅人
    • Organizer
      第42回中部化学関係学協会支部連合秋季大会
    • Place of Presentation
      長野
    • Year and Date
      2011-11-05
  • [Presentation] A New sp2N-Bidentate Ligand, Naph-diPIM2011

    • Author(s)
      M. Kitamura
    • Organizer
      The 15th Korea-Japan Organic Chemistry Symposium
    • Place of Presentation
      Gyeongju-si
    • Year and Date
      2011-10-01
  • [Presentation] Catalytic Dehydrative S-Allylation to ward Synthetic Biology2011

    • Author(s)
      M. Kitamura
    • Organizer
      The 14th Asian Chemical Congress 2011
    • Place of Presentation
      Bangkok
    • Year and Date
      2011-09-07
  • [Presentation] Donor-Acceptor Bifunctional Catalyst : DACat2011

    • Author(s)
      M. Kitamura
    • Organizer
      Shanghai Institute of Organic Chemistry
    • Place of Presentation
      Shanghai
    • Year and Date
      2011-08-16
  • [Presentation] Metathesis-type Donor-Acceptor Bifunctional Catalyst(DACat) and Redox-type DACat2011

    • Author(s)
      M. Kitamura
    • Organizer
      Lanzhou Institute for Chemical Physics
    • Place of Presentation
      Lanzhou
    • Year and Date
      2011-08-10
  • [Presentation] Donor-Acceptor Bifunctional Catalyst2011

    • Author(s)
      M. Kitamura
    • Organizer
      2nd Annual World Congress of Catalytic Asymmetric Synthesis
    • Place of Presentation
      Beijing
    • Year and Date
      2011-08-10
  • [Presentation] レドックス介在型ドナー・アクセプター二官能性触媒2011

    • Author(s)
      北村雅人
    • Organizer
      第44回有機金属若手の会
    • Place of Presentation
      神戸
    • Year and Date
      2011-07-11
  • [Presentation] 脱水型触媒的不斉アリル化2011

    • Author(s)
      北村雅人
    • Organizer
      九州大学大学院「先端有機化学」講演会
    • Place of Presentation
      福岡
    • Year and Date
      2011-07-04
  • [Presentation] Synthesis ofα-Amino Phosphonic Acid-Containing Peptides2010

    • Author(s)
      M. Kitamura
    • Organizer
      Japan Korea Symposium
    • Place of Presentation
      Nara
    • Year and Date
      20101001-03
  • [Presentation] Donor-Acceptor Bifunctional Catalyst : DACat2010

    • Author(s)
      M. Kitamura
    • Organizer
      The 27^<th> Seminaron Synthetic Organic Chemistry
    • Place of Presentation
      Kobe
    • Year and Date
      20100902-04
  • [Presentation] Donor-Acceptor Bifunctional Catalyst : DACat2010

    • Author(s)
      M. Kitamura
    • Organizer
      Inaugural Conference on Molceular & Functional Catalysis(ICMFC-1) Resort Worlds
    • Place of Presentation
      Sentosa, Singapore
    • Year and Date
      20100711-15
  • [Presentation] Donor-Acceptor Bifunctional Catalyst(DACat) From DAIB-Zn to Ph-BINAN-H-Py-Ru and CpRuAllQA2009

    • Author(s)
      M. Kitamura
    • Organizer
      International Symposium on Catalysis and Fine Chemicals
    • Place of Presentation
      Seoul
    • Year and Date
      20091213-17
  • [Presentation] ドナー・アクセプター二官能性触媒.環境調和型有機合成法の開拓に向けて.2009

    • Author(s)
      北村雅人
    • Organizer
      第40回中部化学関係学協会支部連合秋季大会特別討論会
    • Place of Presentation
      岐阜
    • Year and Date
      20091107-08
  • [Presentation] レドックス介在型ドナー・アクセプター二官能性触媒2009

    • Author(s)
      北村雅人
    • Organizer
      日本化学会第89春季年会
    • Place of Presentation
      Tokyo
    • Year and Date
      20090327-30
  • [Presentation] Goodwin-Lions型sp^2N/sp^3N混合系配位子Ph-BINAN-H-Py-ルテニウム錯体の不斉水素化機能.2009

    • Author(s)
      M, Kitamura
    • Organizer
      第四回物質合成シンポジウム
    • Place of Presentation
      Nagoya
    • Year and Date
      20090123-24
  • [Book] 化学の要点シリーズ酸化還元反応2012

    • Author(s)
      佐藤一彦,北村雅人
    • Total Pages
      1-165
    • Publisher
      共立出版
  • [Book] レアメタル便覧第22章化学工業におけるレアメタル, 22. 1節触媒, 22. 1g項還元反応(金田清臣第22章編集幹事)2010

    • Author(s)
      吉村正宏,北村雅人
    • Total Pages
      46-48
    • Publisher
      丸善
  • [Book] In Science of Synthesis, Houben-Weyl Methods of Molecular Transformations2009

    • Author(s)
      M. Kitamura
    • Total Pages
      48
    • Publisher
      Thieme

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Published: 2013-07-31  

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