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Development of Environmentally Benign Biaryl Couplings Based on Nickel Catalysts

Research Project

Project/Area Number 22750040
Research Category

Grant-in-Aid for Young Scientists (B)

Allocation TypeSingle-year Grants
Research Field Organic chemistry
Research InstitutionOsaka University

Principal Investigator

HIRANO Koji  大阪大学, 大学院・工学研究科, 助教 (70532696)

Project Period (FY) 2010 – 2012
Project Status Completed (Fiscal Year 2012)
Budget Amount *help
¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000)
Fiscal Year 2011: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000)
Fiscal Year 2010: ¥2,600,000 (Direct Cost: ¥2,000,000、Indirect Cost: ¥600,000)
Keywords有機合成化学 / 有機金属化学 / ニッケル / 銅 / ホウ素 / ケイ素 / アリール化 / 炭素-水素結合直接変換 / アゾール / ヘテロビアリール / アリールアミン / 直接アリール化 / 酸化カップリング / 求電子的アミノ化 / フルオロアレーン / ビアリール / 直接アリル化 / 直接アミノ化
Research Abstract

We have developed nickel-catalyzed oxidative direct biaryl couplings of heteroarenes with arylsilanes and arylboronic acids via C-H bond cleavage. The above catalysis enables the halogen-free construction of biaryl structures. Relevant new transformations of heteroarenes such as direct alkynylation, allylation, and alkylation were also achieved. Moreover, we succeeded in the copper-mediated dehydrogenative cross-biaryl couplings via two-fold C-H cleavage.

Report

(3 results)
  • 2012 Final Research Report ( PDF )
  • 2011 Annual Research Report
  • 2010 Annual Research Report
  • Research Products

    (53 results)

All 2013 2012 2011 2010 Other

All Journal Article (37 results) (of which Peer Reviewed: 37 results) Presentation (13 results) (of which Invited: 2 results) Remarks (3 results)

  • [Journal Article] Copper-Catalyzed Electrophilic Amination of Arylsilanes with Hydroxylamines2013

    • Author(s)
      Yuya Miki
    • Journal Title

      Organic Letters

      Volume: 15 Issue: 1 Pages: 172-175

    • DOI

      10.1021/ol303222s

    • Related Report
      2011 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Copper-Mediated C-H/C-H Biaryl Coupling of Benzoic Acid Derivatives and 1,3-Azoles2013

    • Author(s)
      Mayuko Nishino
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 52 Issue: 16 Pages: 4457-4461

    • DOI

      10.1002/anie.201300587

    • Related Report
      2011 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Copper-Catalyzed Amination of Ketene Silyl Acetals with Hydroxylamines: Electrophilic Amination Approach to α-Amino Acids2012

    • Author(s)
      松田直樹、平野康次、佐藤哲也、三浦雅博
    • Journal Title

      Angew. Chem., Int. Ed

      Volume: 51巻 Pages: 11827-11831

    • Related Report
      2012 Final Research Report
    • Peer Reviewed
  • [Journal Article] Copper-Mediated Oxidative Direct C-C (Hetero)Aromatic Cross-Coupling2012

    • Author(s)
      平野康次、三浦雅博
    • Journal Title

      Chem. Commun

      Volume: 48巻 Pages: 10704-10714

    • Related Report
      2012 Final Research Report
    • Peer Reviewed
  • [Journal Article] Copper-Mediated and Copper-Catalyzed Cross-Coupling of Indoles and 1,3-Azoles: Double C-H Activation2012

    • Author(s)
      西野真佑子、平野康次、佐藤哲也、三浦雅博
    • Journal Title

      Angew. Chem., Int. Ed

      Volume: 51巻 Pages: 6993-6997

    • Related Report
      2012 Final Research Report
    • Peer Reviewed
  • [Journal Article] Copper-Catalyzed Amination of Arylboronates with N,N-Dialkylhydroxylamines2012

    • Author(s)
      松田直樹、平野康次、佐藤哲也、三浦雅博
    • Journal Title

      Angew. Chem., Int. Ed

      Volume: 51巻 Pages: 3642-3645

    • Related Report
      2012 Final Research Report
    • Peer Reviewed
  • [Journal Article] Nickel- and Cobalt-Catalyzed Direct Alkylation of Azoles with N-Tosylhydrazones Bearing Unactivated Alkyl Groups2012

    • Author(s)
      八尾朋侑、平野康次、佐藤哲也、三浦雅博
    • Journal Title

      Angew. Chem., Int. Ed

      Volume: 51巻 Pages: 775-779

    • Related Report
      2012 Final Research Report
    • Peer Reviewed
  • [Journal Article] An Annulative Electrophilic Amination Approach to 3-Aminobenzoheteroles2012

    • Author(s)
      Naoki Matsuda
    • Journal Title

      Journal of Organic Chemistry

      Volume: 77 Issue: 1 Pages: 617-625

    • DOI

      10.1021/jo202207s

    • Related Report
      2011 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Nickel- and Cobalt-Catalyzed Direct Alkylation of Azoles with N-Tosylhydrazones Bearing Unactivated Alkyl Groups2012

    • Author(s)
      Tomoyuki Yao
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 51 Issue: 3 Pages: 775-779

    • DOI

      10.1002/anie.201106825

    • Related Report
      2011 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis of N-Azolylindoles by Copper-Catalyzed C-H/N-H Coupling-Annulation Sequence of o-Alkynylanilines2012

    • Author(s)
      Yoshiro Oda
    • Journal Title

      Organic Letters

      Volume: 14 Issue: 2 Pages: 664-667

    • DOI

      10.1021/ol203392r

    • Related Report
      2011 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Copper-Catalyzed Direct Amination of Polyfluoroarenes and Azoles with Hydroxylamines and Its Application to the Synthesis of 3-Aminobenzoheteroles2012

    • Author(s)
      Naoki Matsuda
    • Journal Title

      Synthesis

      Volume: 44 Issue: 12 Pages: 1792-1797

    • DOI

      10.1055/s-0031-1289715

    • Related Report
      2011 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Copper-Catalyzed Amination of Arylboronates with N,N-Dialkylhydroxylamines2012

    • Author(s)
      Naoki Matsuda
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 51 Issue: 15 Pages: 3642-3645

    • DOI

      10.1002/anie.201108773

    • Related Report
      2011 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Dehydrogenative Synthesis of C3-Azolylindoles via Copper-Promoted Annulative Direct Coupling of o-Alkynylanilines2012

    • Author(s)
      Yoshiro Oda
    • Journal Title

      Synthesis

      Volume: 44 Issue: 10 Pages: 1515-1520

    • DOI

      10.1055/s-0031-1290965

    • Related Report
      2011 Annual Research Report
    • Peer Reviewed
  • [Journal Article] A Concise Access to (Polyfluoroaryl)allenes by Cu-Catalyzed Direct Coupling with Propargyl Phosphates2012

    • Author(s)
      Akihiro Nakatani
    • Journal Title

      Organic Letters

      Volume: 14 Issue: 10 Pages: 2586-2589

    • DOI

      10.1021/ol300886k

    • Related Report
      2011 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Copper-Mediated and Copper-Catalyzed Cross-Coupling of Indoles and 1,3-Azoles: Double C-H Activation2012

    • Author(s)
      Mayuko Nishino
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 51 Issue: 28 Pages: 6993-6997

    • DOI

      10.1002/anie.201201491

    • Related Report
      2011 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Copper-Mediated Oxidative Direct C-C (Hetero)Aromatic Cross-Coupling2012

    • Author(s)
      Hirano, Koji
    • Journal Title

      Chemical Communications

      Volume: 48 Issue: 87 Pages: 10704-10714

    • DOI

      10.1039/c2cc34659a

    • Related Report
      2011 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Copper-Catalyzed Amination of Ketene Silyl Acetals with Hydroxylamines: Electrophilic Amination Approach to α-Amino Acids2012

    • Author(s)
      Naoki Matsuda
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 51 Issue: 47 Pages: 11827-11831

    • DOI

      10.1002/anie.201206755

    • Related Report
      2011 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Stereospecific Copper-Catalyzed C-H Allylation of Electron-Deficient Arenes with Allyl Phosphates2011

    • Author(s)
      八尾朋侑、平野康次、佐藤哲也、三浦雅博
    • Journal Title

      Angew. Chem., Int. Ed

      Volume: 50巻 Pages: 2990-2994

    • Related Report
      2012 Final Research Report
    • Peer Reviewed
  • [Journal Article] Copper-Mediated Intermolecular Direct Biaryl Coupling2011

    • Author(s)
      北原雅典、梅田伸好、平野康次、佐藤哲也、三浦雅博
    • Journal Title

      J. Am. Chem. Soc

      Volume: 133巻 Pages: 2160-2162

    • Related Report
      2012 Final Research Report
    • Peer Reviewed
  • [Journal Article] Copper-Catalyzed Annulative Amination of ortho-Alkynylphenols with Hydroxylamines: Synthesis of 3-Aminobenzofurans by Umpolung Amination Strategy2011

    • Author(s)
      Koji Hirano
    • Journal Title

      Organic Letters

      Volume: 13 Issue: 9 Pages: 2395-2397

    • DOI

      10.1021/ol200651r

    • Related Report
      2011 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Copper-Catalyzed Direct Amination of Electron-Deficient Arenes with Hydroxylamines2011

    • Author(s)
      Naoki Matsuda
    • Journal Title

      Organic Letters

      Volume: 13 Issue: 11 Pages: 2860-2863

    • DOI

      10.1021/ol200855t

    • Related Report
      2011 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Copper-Mediated Annulative Direct Coupling of o-Alkynylphenols with Oxadiazoles: A Dehydrogenative Cascade Construction of Biheteroaryls2011

    • Author(s)
      Hitoshi Hachiya
    • Journal Title

      Organic Letters

      Volume: 13 Issue: 12 Pages: 3076-3079

    • DOI

      10.1021/ol200975j

    • Related Report
      2011 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Copper-Catalyzed Oxidative Direct Cyclization of N-Methylanilines with Electron-Deficient Alkenes Using Molecular Oxygen2011

    • Author(s)
      Nishino, Mayuko
    • Journal Title

      The Journal of Organic Chemistry

      Volume: 76 Issue: 15 Pages: 6447-6451

    • DOI

      10.1021/jo2011329

    • Related Report
      2011 Annual Research Report
    • Peer Reviewed
  • [Journal Article] A remarkable effect of ionic liquids in transition-metal-free aerobic oxidation of benzylic alcohols2011

    • Author(s)
      Yoshiro Oda
    • Journal Title

      Tetrahedron Letters

      Volume: 52 Issue: 41 Pages: 5392-5394

    • DOI

      10.1016/j.tetlet.2011.08.053

    • Related Report
      2011 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Copper-Catalyzed Direct Sulfoximination of Azoles and Polyfluoroarenes under Ambient Conditions2011

    • Author(s)
      Mitsuru Miyasaka
    • Journal Title

      Organic Letters

      Volume: 13 Pages: 359-361

    • Related Report
      2010 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Copper-Mediated Intermolecular Direct Biaryl Coupling2011

    • Author(s)
      Masanori Kitahara
    • Journal Title

      Journal of the American Chemical Society

      Volume: 133 Pages: 2160-2162

    • Related Report
      2010 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Stereospecific Copper-Catalyzed C-H Allylation of Electron-Deficient Arenes with Allyl Phosphates2011

    • Author(s)
      Tomoyuki Yao
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 50 Pages: 2990-2994

    • Related Report
      2010 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Direct Carbon-Hydrogen Bond Functionalization of Heterocyclic Compounds2011

    • Author(s)
      Koji Hirano
    • Journal Title

      Synlett

      Pages: 294-307

    • Related Report
      2010 Annual Research Report
    • Peer Reviewed
  • [Journal Article] C-H Functionalization of Heteroarenes Using First-Row Transition Metals : Copper and Nickel Catalyses2011

    • Author(s)
      Koji Hirano
    • Journal Title

      Journal of Synthetic Organic Chemistry, Japan

      Volume: 69 Pages: 252-265

    • NAID

      10027916974

    • Related Report
      2010 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Oxidative Nickel-Air Catalysis in C-H Arylation: Direct Cross-Coupling of Azoles with Arylboronic Acids using Air as Sole Oxidant2010

    • Author(s)
      蜂谷斉士、平野康次、佐藤哲也、三浦雅博
    • Journal Title

      ChemCatChem

      Volume: 2巻 Pages: 1403-1406

    • Related Report
      2012 Final Research Report
    • Peer Reviewed
  • [Journal Article] A New Entry of Amination Reagents for Heteroaromatic C-H Bonds: Copper-Catalyzed Direct Amination of Azoles with Chloroamines at Room Temperature2010

    • Author(s)
      川野剛、平野康次、佐藤哲也、三浦雅博
    • Journal Title

      J. Am. Chem. Soc

      Volume: 132巻 Pages: 6900-6901

    • Related Report
      2012 Final Research Report
    • Peer Reviewed
  • [Journal Article] Nickel- and Copper-Catalyzed Direct Alkynylation of Azoles and Polyfluoroarenes with Terminal Alkynes under O_2 or Atmospheric Conditions2010

    • Author(s)
      Naoto Matsuyama
    • Journal Title

      Organic Letters

      Volume: 12 Pages: 2358-2361

    • Related Report
      2010 Annual Research Report
    • Peer Reviewed
  • [Journal Article] A New Entry of Amination Reagents for Heteroaromatic C-H Bonds : Copper-Catalyzed Direct Amination of Azoles with Chloroamines at Room Temperature2010

    • Author(s)
      Tsuyoshi Kawano
    • Journal Title

      Journal of the American Chemical Society

      Volume: 132 Pages: 6900-6901

    • Related Report
      2010 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Palladium-Catalyzed Direct Oxidative Alkenylation of Azoles2010

    • Author(s)
      Mitsuru Miyasaka
    • Journal Title

      Journal of Organic Chemistry

      Volume: 75 Pages: 5421-5424

    • Related Report
      2010 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Oxidative Nickel-Air Catalysis in C-H Arylation : Direct Cross-Coupling of Azoles with Arylboronic Acids using Air as Sole Oxidant2010

    • Author(s)
      Hitoshi Hachiya
    • Journal Title

      ChemCatChem

      Volume: 39 Pages: 1403-1406

    • Related Report
      2010 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Palladium Nanoparticles in Ionic Liquid by Sputter Deposition as Catalysts for Suzuki-Miyaura Coupling in Water2010

    • Author(s)
      Yoshiro Oda
    • Journal Title

      Chemistry Letters

      Volume: 132 Pages: 1069-1071

    • Related Report
      2010 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Palladium- and Nickel-Catalyzed Direct Alkylation of Azoles with Unactivated Alkyl Bromides and Chlorides2010

    • Author(s)
      Tomoyuki Yao
    • Journal Title

      Chemistry-A European Journal

      Volume: 16 Pages: 12307-12311

    • Related Report
      2010 Annual Research Report
    • Peer Reviewed
  • [Presentation] 求電子的アミノ化試薬を活用する新規触媒的炭素-窒素結合形成反応の開発2013

    • Author(s)
      平野康次
    • Organizer
      日本化学会第93 春季年会(2013)若い世代の特別講演会
    • Place of Presentation
      立命館大学
    • Year and Date
      2013-03-23
    • Related Report
      2012 Final Research Report
  • [Presentation] Copper-Catalyzed Electrophilic Amination: An Umpolung Strategy for C-N Bond Formations2013

    • Author(s)
      平野康次
    • Organizer
      BIOTECHNOLOGY AND CHEMISTORY FOR GREEN GROWTH (JSPS Japanese-German Graduate Externship Program)
    • Place of Presentation
      千里ライフサイエンスセンター
    • Year and Date
      2013-03-12
    • Related Report
      2012 Final Research Report
  • [Presentation] 求電子的アミノ化試薬を活用する新規触媒的炭素-窒素結合形成反応の開発2013

    • Author(s)
      平野康次
    • Organizer
      第1回卓越拠点有機若手ワークショップ
    • Place of Presentation
      京都大学
    • Year and Date
      2013-03-07
    • Related Report
      2012 Final Research Report
  • [Presentation] 遷移金属触媒を用いたアゾール類の直接アルキル化反応2012

    • Author(s)
      平野康次、八尾朋侑、向井智哉、佐藤哲也、三浦雅博
    • Organizer
      日本化学会第92春季年会(2012)
    • Place of Presentation
      慶応大学
    • Year and Date
      2012-03-27
    • Related Report
      2012 Final Research Report
  • [Presentation] Copper-Mediated Dehydrogenative Direct Biaryl Couplings2011

    • Author(s)
      北原雅典、梅田伸好、蜂谷斉士、平野康次、佐藤哲也、三浦雅博
    • Organizer
      The Seventh International Symposium on Integrated Synthesis (ISIS-7)
    • Place of Presentation
      シーサイドホテル舞子ビラ神戸
    • Year and Date
      2011-10-10
    • Related Report
      2012 Final Research Report
  • [Presentation] 銅触媒を用いた求電子的アミノ化試薬によるヘテロ芳香族アミン類の合成2011

    • Author(s)
      平野康次、松田直樹、佐藤哲也、三浦雅博
    • Organizer
      第58回有機金属化学討論会
    • Place of Presentation
      名古屋大学
    • Year and Date
      2011-09-08
    • Related Report
      2012 Final Research Report
  • [Presentation] Nickel-Catalyzed Direct Arylation of Heteroarenes with Arylsilanes and -borons2010

    • Author(s)
      蜂谷斉士、平野康次、佐藤哲也、三浦雅博
    • Organizer
      The Sixth International Symposium on Integrated Synthesis (ISIS-6)
    • Place of Presentation
      シーサイドホテル舞子ビラ神戸
    • Year and Date
      2010-10-24
    • Related Report
      2012 Final Research Report 2010 Annual Research Report
  • [Presentation] 銅触媒を用いた求電子的アミノ化試薬によるヘテロ芳香族アミン類の合成

    • Author(s)
      平野康次
    • Organizer
      第58回有機金属化学討論会
    • Place of Presentation
      名古屋大学
    • Related Report
      2011 Annual Research Report
  • [Presentation] 遷移金属触媒を用いたアゾール類の直接アルキル化反応

    • Author(s)
      平野康次
    • Organizer
      日本化学会第92春季年会(2012)
    • Place of Presentation
      慶応大学
    • Related Report
      2011 Annual Research Report
  • [Presentation] 求電子的アミノ化試薬を活用する新規触媒的炭素―窒素結合形成反応の開発

    • Author(s)
      平野康次
    • Organizer
      第1回卓越拠点有機若手ワークショップ
    • Place of Presentation
      京都大学
    • Related Report
      2011 Annual Research Report
    • Invited
  • [Presentation] Copper-Catalyzed Electrophilic Amination: An Umpolung Strategy for C-N Bond Formations

    • Author(s)
      平野康次
    • Organizer
      BIOTECHNOLOGY AND CHEMISTORY FOR GREEN GROWTH (JSPS Japanese-German Graduate Externship Program
    • Place of Presentation
      千里ライフサイエンスセンター
    • Related Report
      2011 Annual Research Report
  • [Presentation] Copper-Mediated Dehydrogenative Direct Biaryl Couplings

    • Author(s)
      平野康次
    • Organizer
      The Seventh International Symposium on Integrated Synthesis (ISIS-7)
    • Place of Presentation
      シーサイドホテル舞子ビラ神戸
    • Related Report
      2011 Annual Research Report
  • [Presentation] 求電子的アミノ化試薬を活用する新規触媒的炭素―窒素結合形成反応の開発

    • Author(s)
      平野康次
    • Organizer
      日本化学会第93春季年会(2013)若い世代の特別講演会
    • Place of Presentation
      立命館大学
    • Related Report
      2011 Annual Research Report
    • Invited
  • [Remarks]

    • URL

      http://www.chem.eng.osaka-u.ac.jp/~miura-lab/

    • Related Report
      2012 Final Research Report
  • [Remarks] ホームページ

    • URL

      http://www.chem.eng.osaka-u.ac.jp/~miura-lab/

    • Related Report
      2011 Annual Research Report
  • [Remarks]

    • URL

      http://www.chem.eng.osaka-u.ac.jp/~miura-lab/

    • Related Report
      2010 Annual Research Report

URL: 

Published: 2010-08-23   Modified: 2016-04-21  

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