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脱水型不斉TsujiーTrost反応の開発

Publicly Offered Research

Project AreaOrganic Synthesis based on Integration of Chemical Reactions. New Methodologies and New Materials
Project/Area Number 24106713
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

北村 雅人  名古屋大学, 創薬科学研究科, 教授 (50169885)

Project Period (FY) 2012-04-01 – 2014-03-31
Project Status Completed (Fiscal Year 2013)
Budget Amount *help
¥6,760,000 (Direct Cost: ¥5,200,000、Indirect Cost: ¥1,560,000)
Fiscal Year 2013: ¥3,380,000 (Direct Cost: ¥2,600,000、Indirect Cost: ¥780,000)
Fiscal Year 2012: ¥3,380,000 (Direct Cost: ¥2,600,000、Indirect Cost: ¥780,000)
Keywordsルテニウム / 不斉アリル化 / ヘテロ環 / 脱水反応 / 脱水型アリル化 / 不斉反応 / 遷移金属錯体触媒
Research Abstract

前年度までに開発したキラルなピコリン酸型配位子Cl-Naph-PyCOOH(6-(2-chloro- naphthalen-1-yl)-5-methylpyridine-2-carboxylic acid)のモノカチオン性CpRu(II)錯体は,w位に酸素や窒素求核原子を置換する様々なアリルアルコール類を定量的かつ高エナンチオ選択的に対応するaアルケニル環状化合物に変換することができる.この脱水型分子内不斉アリル化によって得られるヘテロ環状化合物はいずれも生理活性天然物合成におけるキラル鍵中間体として重要である.本年度は,本触媒反応の高活性と高エナンチオ選択性発現の機構の解明に照準を置いた.
モデル系におけるRu(IV)πアリル錯体の単離・構造解析,NMR実験,重水素標識実験の結果をもとに本反応の触媒サイクルを推定した.[CpRu(II)(CH3CN)3]PF6 (I)と(R)-Cl-Naph-PyCOOHから生じる錯体Aにおいて、ソフトなRuとハードなプロトンがそれぞれアリルアルコール基質のオレフィン部とヒドロキシ酸素原子と相互作用して基質/触媒複合体Bへと移行する.ここでドナー・アクセプター二官能性触媒(DACat)機能が働いて,Ru側(インサイド)にH2Oを脱離して,πアリル錯体Cとなる.π-σ-π平衡下,立体反発のない最も安定なπアリル錯体C’へと異性化後,求核部がカルボキシラト酸素原子側からアリル炭素原子をインサイド攻撃して生成物/触媒複合体Dを与える.アリル化生成物を放出するとともにAが再生して触媒サイクルが完結する.サイクル上の活性種は多くの不活性種と平衡関係にあり,反応系は単純ではない.Cl-Naph-PyCOOH配位子の「Cl基」がCp水素原子と相互作用して,CpRu(II)の求核性を向上し,COOHがアリルアルコール基質の求電子性を向上する.極微量,系内に発生するこのDACat種Bが高性能発現の鍵を握っていると考えている.

Current Status of Research Progress
Reason

25年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

25年度が最終年度であるため、記入しない。

Report

(2 results)
  • 2013 Annual Research Report
  • 2012 Annual Research Report
  • Research Products

    (22 results)

All 2014 2013 2012

All Journal Article (6 results) (of which Peer Reviewed: 6 results) Presentation (12 results) (of which Invited: 9 results) Book (4 results)

  • [Journal Article] Asymmetric Hydrogenation of tert-Alkyl Ketones: DMSO Effect in Unification of Stereoisomeric Ruthenium Complexes2013

    • Author(s)
      Tomoya Yamamura, Hiroshi Nakatsuka, Shinji Tanaka, Masato Kitamura
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 52 Issue: 35 Pages: 9313-9315

    • DOI

      10.1002/anie.201304408

    • Related Report
      2013 Annual Research Report
    • Peer Reviewed
  • [Journal Article] CpRu-catalyzed asymmetric dehydrative allylation2013

    • Author(s)
      Masato Kitamura, Kengo Miyata, Tomoaki Seki, Namdev Vatmurge, Shinji Tanaka
    • Journal Title

      Pure and Applied Chemistry

      Volume: 85 Issue: 6 Pages: 1121-1132

    • DOI

      10.1351/pac-con-12-10-02

    • Related Report
      2013 Annual Research Report 2012 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Reaction of Frustrated Lewis Pairs with Ketones and Esters2012

    • Author(s)
      Bao-Hua Xu, Raul Alfonso Adler Yanez, Hiroshi Nakatsuka, Masato Kitamura, Roland Frohlich, Gerald Kehr, Gerhard Erker
    • Journal Title

      Chemistry-An Asian Journal

      Volume: 7 Issue: 6 Pages: 1347-1356

    • DOI

      10.1002/asia.201100960

    • Related Report
      2012 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Double Arylation of Acetylenedicarboxylate with B(C_6F_5)_32012

    • Author(s)
      Hiroshi Nakatsuka, Roland Frohlich, Masato Kitamura, Gerald Kehr, Gerhard Erker
    • Journal Title

      European Journal of Inorganic Chemistry

      Volume: 8 Issue: 8 Pages: 1163-1166

    • DOI

      10.1002/ejic.201101413

    • Related Report
      2012 Annual Research Report
    • Peer Reviewed
  • [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 Issue: 14 Pages: 608-611

    • DOI

      10.1055/s-0031-1290301

    • Related Report
      2012 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Enantioselective Synthesis of Pyrrolidine-, Piperidine-, and Azepane-type N-Heterocycles with α-Alkenyl Substitution : the CpRu-Catalyzed Dehydrative Intramolecular N-Allylation Approach2012

    • Author(s)
      Tomoaki Seki, Shinji Tanaka, Masato Kitamura
    • Journal Title

      Organic Letters

      Volume: 14 Issue: 2 Pages: 608-611

    • DOI

      10.1021/ol203218d

    • Related Report
      2012 Annual Research Report
    • Peer Reviewed
  • [Presentation] 脱水型不斉Tsuji-Trost反応の開発2014

    • Author(s)
      北村雅人
    • Organizer
      集積反応化学公開シンポジウム
    • Place of Presentation
      東京
    • Related Report
      2013 Annual Research Report
  • [Presentation] 脱水型不斉Tsuji-Trost反応の開発2014

    • Author(s)
      北村雅人
    • Organizer
      集積反応化学平成25年度第2回成果報告会
    • Place of Presentation
      東京
    • Related Report
      2013 Annual Research Report
  • [Presentation] 触媒的不斉水素化の開発・応用・機構解明2013

    • Author(s)
      北村雅人
    • Organizer
      平成25年度有機合成化学後期(秋期)講習会
    • Place of Presentation
      東京
    • Related Report
      2013 Annual Research Report
    • Invited
  • [Presentation] Development of Magnetically Separable Heterogeneous Deallylation Catalyst2013

    • Author(s)
      S. Tanaka, M. Kitamura
    • Organizer
      The 16th International Symposium on Relations Between Homogeneous ond Heterogeneous Catalysis
    • Place of Presentation
      Sapporo
    • Related Report
      2013 Annual Research Report
  • [Presentation] Design and Synthesis of Linear N4 Chiral Ligands: Its Application to Asymmetric Hydrogenation of Aromatic Ketones2012

    • Author(s)
      吉村正宏・北村雅人
    • Organizer
      Cambodian Malaysian Chemical Conference (CMCC) 2012
    • Place of Presentation
      Angkor Century Resort Spa, Siem Reap, Cambodia
    • Year and Date
      2012-10-19
    • Related Report
      2012 Annual Research Report
    • Invited
  • [Presentation] CpRu-Catalyzed Dehydrative Allylation of Thiols and Application for Peptide Modification.2012

    • Author(s)
      田中慎二・北村雅人
    • Organizer
      17th Malaysian Chemical Congress
    • Place of Presentation
      la Lumpure, Malaysia
    • Year and Date
      2012-10-15
    • Related Report
      2012 Annual Research Report
    • Invited
  • [Presentation] New Chiral sp2N Bidentate Ligand: Naph-diPIM-dioxo-R ―Donor-Acceptor Bifunctional Catalyst―2012

    • Author(s)
      北村雅人
    • Organizer
      The 6th Takeda Science Foundation Symposium on PharmaSciences
    • Place of Presentation
      Osaka
    • Year and Date
      2012-09-13
    • Related Report
      2012 Annual Research Report
    • Invited
  • [Presentation] A New sp2N Bidentate Ligand2012

    • Author(s)
      北村雅人
    • Organizer
      The 2nd International Conference on Molecular and Functional Catalysis
    • Place of Presentation
      Singapore
    • Year and Date
      2012-07-30
    • Related Report
      2012 Annual Research Report
    • Invited
  • [Presentation] 脱水型不斉Tsuji#8211;Trost反応2012

    • Author(s)
      北村雅人
    • Organizer
      第24回万有シンポジウム―有機合成化学の最前線―
    • Place of Presentation
      札幌
    • Year and Date
      2012-07-07
    • Related Report
      2012 Annual Research Report
    • Invited
  • [Presentation] CpRu#8211;Catalyzed Asymmetric Dehydrative Allylation2012

    • Author(s)
      北村雅人
    • Organizer
      19th International Conference on Organic Synthesis and 24th Royal Australian Institute Organic Conference
    • Place of Presentation
      Melbourne
    • Year and Date
      2012-07-01
    • Related Report
      2012 Annual Research Report
    • Invited
  • [Presentation] 2001年ノーベル賞 ―右手型と左手型の分子をつくり分ける―2012

    • Author(s)
      北村雅人
    • Organizer
      あいちサイエンスフェスティバル
    • Place of Presentation
      豊橋
    • Year and Date
      2012-06-09
    • Related Report
      2012 Annual Research Report
    • Invited
  • [Presentation] A New Method for Lipidation of Cysteine-containing Peptides2012

    • Author(s)
      田中慎二・Jaisankar,P.・北村雅人
    • Organizer
      第3回統合物質シンポジウム
    • Place of Presentation
      九州大学
    • Year and Date
      2012-06-01
    • Related Report
      2012 Annual Research Report
    • Invited
  • [Book] e-EROS2013

    • Author(s)
      Masato Kitamura
    • Total Pages
      1
    • Publisher
      Ferrocene, 1,1'-bis[(2R,4R)-2,4-diethyl-1-phosphetanyl]-, stereoisomer; Ferrocene, 1,1'-bis[(2S,4S)-2,4-diethyl-1-phosphetanyl]-, stereoisomer, RN01622
    • Related Report
      2012 Annual Research Report
  • [Book] Comprehensive Chirality2012

    • Author(s)
      Masaki Tsukamoto, Masato Kitamura
    • Total Pages
      4
    • Publisher
      Reduction #8211; Hydrogenation: C #9552; C; Chemoselective.
    • Related Report
      2012 Annual Research Report
  • [Book] Comprehensive Chirality2012

    • Author(s)
      Seiji Suga, Masato Kitamura
    • Total Pages
      5
    • Publisher
      Asymmetric 1,2-Addition of Organometallics to Carbonyl and Imine Groups.
    • Related Report
      2012 Annual Research Report
  • [Book] 化学の要点シリーズ2012

    • Author(s)
      佐藤一彦・北村雅人
    • Total Pages
      165
    • Publisher
      酸化還元反応
    • Related Report
      2012 Annual Research Report

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Published: 2013-05-15   Modified: 2019-07-29  

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