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Challenge for Development of Catalytic Enantioselective Hydrofluorination and Hydrotrifluoromethylation of Alkenes

Research Project

Project/Area Number 15K13696
Research Category

Grant-in-Aid for Challenging Exploratory Research

Allocation TypeMulti-year Fund
Research Field Synthetic chemistry
Research InstitutionOsaka University

Principal Investigator

Hirano Koji  大阪大学, 工学研究科, 准教授 (70532696)

Project Period (FY) 2015-04-01 – 2017-03-31
Project Status Completed (Fiscal Year 2016)
Budget Amount *help
¥3,900,000 (Direct Cost: ¥3,000,000、Indirect Cost: ¥900,000)
Fiscal Year 2016: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Fiscal Year 2015: ¥2,470,000 (Direct Cost: ¥1,900,000、Indirect Cost: ¥570,000)
Keywordsフッ素 / 銅触媒 / リン / 触媒的不斉合成 / 有機フッ素化合物 / 有機リン化合物
Outline of Final Research Achievements

The purpose of this research is development of highly challenging catalytic enantioselective hydrofluorination and hydrotrifluoromethylation of alkenes. While preliminary, we have developed a nonenantioselective copper-based catalyst system for the catalytic hydrofluorination of alkenes. To increase the catalytic performance and establish the enantioselective variant, we have also developed a new copper-catalyzed C-P bond-forming reaction for the synthesis of novel and highly active ligands. By this Cu catalysis, we can obtain bisphosphine-type ligands from simple and readily available terminal alkenes in one shot.

Report

(3 results)
  • 2016 Annual Research Report   Final Research Report ( PDF )
  • 2015 Research-status Report
  • Research Products

    (25 results)

All 2017 2016 2015

All Journal Article (16 results) (of which Peer Reviewed: 16 results,  Acknowledgement Compliant: 16 results) Presentation (8 results) (of which Int'l Joint Research: 4 results,  Invited: 6 results) Book (1 results)

  • [Journal Article] Rhodium-Catalyzed Electrophilic Amination of Arylboronic Acids with Secondary Hydroxylamines2017

    • Author(s)
      Tomohiro Yasuhisa, Koji Hirano, Masahiro Miura
    • Journal Title

      Chemistry Letters

      Volume: 46 Issue: 4 Pages: 463-465

    • DOI

      10.1246/cl.161158

    • NAID

      130005549121

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Iridium-Catalyzed Site-Selective C-H Borylation of 2-Pyridones2017

    • Author(s)
      Wataru Miura, Koji Hirano, Masahiro Miura
    • Journal Title

      Synthesis

      Volume: 49 Issue: 21 Pages: 4745-4752

    • DOI

      10.1055/s-0036-1588735

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Copper-Mediated Decarboxylative Coupling of Benzamides with ortho-Nitrobenzoic Acids via Directed C-H Cleavage2017

    • Author(s)
      Kazutaka Takamatsu, Koji Hirano, Masahiro MIura
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 56 Issue: 19 Pages: 5353-5357

    • DOI

      10.1002/anie.201701918

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Highly C3-Selective Direct Alkylation and Arylation of 2-Pyridones under Visible-light-promoted Photoredox Catalysis2016

    • Author(s)
      Atifah Najib, Sho Tabuchi, Koji Hirano, Masahiro Miura
    • Journal Title

      Heterocycles

      Volume: 92 Issue: 7 Pages: 1187-1203

    • DOI

      10.3987/com-16-13459

    • NAID

      40020879225

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Rhodium-Catalyzed C6-Selective C-H Borylation of 2-Pyridones2016

    • Author(s)
      Wataru Miura, Koji Hirano, Masahiro Miura
    • Journal Title

      Organic Letters

      Volume: 18 Issue: 15 Pages: 3742-3745

    • DOI

      10.1021/acs.orglett.6b01762

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Copper-Catalyzed Intramolecular Benzylic C-H Amination for the Synthesis of Isoindolinones2016

    • Author(s)
      Chiaki Yamamoto, Kazutaka Takamatsu, Koji Hirano, Masahiro Miura
    • Journal Title

      The Journal of Organic Chemistry

      Volume: 81 Issue: 17 Pages: 7675-7684

    • DOI

      10.1021/acs.joc.6b01393

    • NAID

      130005295740

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Copper-Catalyzed Regio- and Stereoselective Aminoboration of Alkenylboronates2016

    • Author(s)
      Daiki Nishikawa, Koji Hirano, Masahiro Miura
    • Journal Title

      Organic Letters

      Volume: 18 Issue: 19 Pages: 4856-4859

    • DOI

      10.1021/acs.orglett.6b02338

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Copper-Catalyzed Vicinal Diphosphination of Styrenes: Access to 1,2-Bis(diphenylphosphino)ethane-Type Bidentate Ligands from Olefins2016

    • Author(s)
      Yuto Okugawa, Koji Hirano, Masahiro MIura
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 55 Issue: 43 Pages: 13558-13561

    • DOI

      10.1002/anie.201606976

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Synthesis of β-Boryl-α-Aminosilanes by Copper-Catalyzed Aminoboration of Vinylsilanes2016

    • Author(s)
      Kodai Kato, Koji Hirano, Masahiro Miura
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 55 Issue: 46 Pages: 14400-14404

    • DOI

      10.1002/anie.201608139

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Copper-Catalyzed Regioselective Ring-Opening Hydroamination of Methylenecyclopropanes2016

    • Author(s)
      Daiki Nishikawa, Koji Hirano, Masahiro Miura
    • Journal Title

      The Journal of Organic Chemistry

      Volume: 81 Issue: 24 Pages: 12128-12134

    • DOI

      10.1021/acs.joc.6b02483

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Palladium-Catalyzed Asymmetric Benzylic Alkylation of Active Methylene Compounds with α-Naphthylbenzyl Carbonates and Pivalates2016

    • Author(s)
      Sho Tabuchi, Koji Hirano, Masahiro Miura
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 印刷中 Issue: 24 Pages: 6973-6977

    • DOI

      10.1002/anie.201602075

    • Related Report
      2015 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Ligand-Controlled Regiodivergent Cu-Catalyzed Aminoboration of Unactivated Terminal Alkenes2015

    • Author(s)
      Ryosuke Sake, Koji Hirano, Masahiro Miura
    • Journal Title

      Journal of the American Chemical Society

      Volume: 137 Issue: 20 Pages: 6460-6463

    • DOI

      10.1021/jacs.5b02775

    • Related Report
      2015 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Copper-Mediated Oxidative Coupling of Benzamides with Maleimides via Directed C-H Cleavage2015

    • Author(s)
      Wataru Miura, Koji Hirano, Masahiro Miura
    • Journal Title

      Organic Letters

      Volume: 17 Issue: 16 Pages: 4034-4037

    • DOI

      10.1021/acs.orglett.5b01940

    • Related Report
      2015 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Copper-Catalyzed Formal [4 + 1] Cycloaddition of Benzamides and Isonitriles via Directed C-H Cleavage2015

    • Author(s)
      Kazutaka Takamatsu, Koji Hirano Masahiro Miura
    • Journal Title

      Organic Letters

      Volume: 17 Issue: 16 Pages: 4066-4069

    • DOI

      10.1021/acs.orglett.5b01986

    • Related Report
      2015 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Stereospecific Pd-Catalyzed Intermolecular C(sp3)-C(sp) Cross-Coupling of Diarylmethyl Carbonates and Terminal Alkynes Under Base-Free Conditions2015

    • Author(s)
      Sho Tabuchi, Koji Hirano, Masahiro Miura
    • Journal Title

      Chemistry-A European Journal

      Volume: 21 Issue: 47 Pages: 16823-16827

    • DOI

      10.1002/chem.201503647

    • Related Report
      2015 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Asymmetric Synthesis of α-Aminoboronic Acid Derivatives by Copper-Catalyzed Enantioselective Hydroamination2015

    • Author(s)
      Daiki Nishikawa, Koji Hirano, Masahiro Miura
    • Journal Title

      Journal of the American Chemical Society

      Volume: 137 Issue: 50 Pages: 15620-15623

    • DOI

      10.1021/jacs.5b09773

    • Related Report
      2015 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Presentation] Catalytic vic-Diphosphination of Terminal Alkenes with Silylphosphine2017

    • Author(s)
      Koji Hirano
    • Organizer
      International Symposium on Pure & Applied Chemistry 2017 (ISPAC2017)
    • Place of Presentation
      Ho Chi Minh City, Vietnam
    • Year and Date
      2017-06-08
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] 銅触媒を用いた窒素およびリン元素導入を伴うアルケンの新規二官能基化反応の開発2016

    • Author(s)
      平野 康次
    • Organizer
      分子研研究会「若い世代が創る次世代型分子触媒の開発とその展望」
    • Place of Presentation
      分子科学研究所(愛知県、岡崎市)
    • Year and Date
      2016-11-10
    • Related Report
      2016 Annual Research Report
    • Invited
  • [Presentation] Synthesis of α-Aminoboronic Acid and -silane Derivatives by Copper-Catalyzed Electrophilic Amination2016

    • Author(s)
      Koji Hirano
    • Organizer
      JSPS Japanese-German Graduate Externship International Symposium "Biological and Chemical Methods for Selective Catalysis"
    • Place of Presentation
      Aachen, Germany
    • Year and Date
      2016-09-05
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research
  • [Presentation] 銅触媒を用いた求電子的アミノ化:”マイナス”を”プラス”にしたら何ができるのか?2016

    • Author(s)
      平野 康次
    • Organizer
      第36回有機合成若手セミナー「明日の有機合成を担う人のために」
    • Place of Presentation
      京都薬科大学(京都府、京都市)
    • Year and Date
      2016-08-09
    • Related Report
      2016 Annual Research Report
    • Invited
  • [Presentation] Development of New Catalytic C-N Bond Formations Based on Electrophilic Amination2016

    • Author(s)
      Koji Hirano
    • Organizer
      日本化学会第96春季年会
    • Place of Presentation
      同志社大学(京都府、京田辺市)
    • Year and Date
      2016-03-24
    • Related Report
      2015 Research-status Report
    • Invited
  • [Presentation] 銅触媒による求電子的アミノ化を利用した炭素ー窒素結合形成2015

    • Author(s)
      Koji Hirano
    • Organizer
      ITbM/IGER Chemistry Workshop ~Symposium of Organic Chemistry by Students~
    • Place of Presentation
      名古屋大学(愛知県、名古屋市)
    • Year and Date
      2015-10-30
    • Related Report
      2015 Research-status Report
    • Invited
  • [Presentation] Regiodivergent Copper-Catalyzed Aminoboration of Unactivated Terminal Alkenes2015

    • Author(s)
      Koji Hirano
    • Organizer
      OMCOS 18
    • Place of Presentation
      Sitges, Barcelona
    • Year and Date
      2015-06-28
    • Related Report
      2015 Research-status Report
    • Int'l Joint Research
  • [Presentation] Regiodivergent Copper-Catalyzed Aminoboration of Unactivated Terminal Alkenes2015

    • Author(s)
      Koji Hirano
    • Organizer
      Organic Chemistry Symposia-Kyoto, RSC Japan Road Show
    • Place of Presentation
      京都大学(京都府、京都市)
    • Year and Date
      2015-06-05
    • Related Report
      2015 Research-status Report
    • Int'l Joint Research / Invited
  • [Book] Copper-Mediated Intermolecular C-H/C-H and C-H/N-H Couplings via Aromatic C-H Cleavage in C-H Bond Activation and Catalytic Functionalization II2015

    • Author(s)
      Koji Hirano, Masahiro Miura
    • Total Pages
      18
    • Publisher
      Springer
    • Related Report
      2015 Research-status Report

URL: 

Published: 2015-04-16   Modified: 2018-03-22  

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