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Concise Synthesis of Organophosphorus Compounds by Development of New Strategies for Generation of Highly Reactive Phosphorus Species

Research Project

Project/Area Number 18K19078
Research Category

Grant-in-Aid for Challenging Research (Exploratory)

Allocation TypeMulti-year Fund
Review Section Medium-sized Section 33:Organic chemistry and related fields
Research InstitutionOsaka University

Principal Investigator

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

Project Period (FY) 2018-06-29 – 2020-03-31
Project Status Completed (Fiscal Year 2019)
Budget Amount *help
¥6,370,000 (Direct Cost: ¥4,900,000、Indirect Cost: ¥1,470,000)
Fiscal Year 2019: ¥2,210,000 (Direct Cost: ¥1,700,000、Indirect Cost: ¥510,000)
Fiscal Year 2018: ¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000)
Keywords有機リン化合物 / リンラジカル / リンカチオン / ビスホスフィン / ホスホール / リン / リンジカチオン / ジベンゾホスホール / ベンゾホスホール
Outline of Final Research Achievements

We have developed new strategies for generation of highly reactive organophosphorus species such as phophinyl radicals and phosphenium cations from readily available and stable starting materials and applied them to regioselective alkene diphosphination and C-H phosphination, directly giving bisphosphines and (di)benzophospholes, respectively. The former can be a good supporting ligand for new transition metal catalysis, and the latter is a potent functional organic molecule such as organic photovoltaic cell.

Academic Significance and Societal Importance of the Research Achievements

リンは現代の有機化学において欠くことのできない重要な典型元素の一つであり、触媒、医農薬品、有機機能性材料等の鍵元素として頻繁に利用されている。しかし、このような状況に反して有機分子にリン元素を導入するための炭素-リン結合形成手法は驚くほど少ない。本研究では、これまでその高すぎる反応性のためにあまり利用されてこなかった高反応性リン化学種の新規発生法の開発を通して新たな炭素-リン結合形成手法を創出し、多数の有用な含リン有機化合物の迅速合成に成功した。本成果は物質創生の点から現在社会の豊かさを支える有機合成化学、特にヘテロ元素化学や材料化学の更なる進展に大きく寄与するものである。

Report

(3 results)
  • 2019 Annual Research Report   Final Research Report ( PDF )
  • 2018 Research-status Report
  • Research Products

    (28 results)

All 2020 2019 2018

All Journal Article (22 results) (of which Int'l Joint Research: 2 results,  Peer Reviewed: 22 results,  Open Access: 1 results) Presentation (5 results) (of which Int'l Joint Research: 4 results,  Invited: 2 results) Book (1 results)

  • [Journal Article] Pyridine-directed Rh-catalyzed C6-selective C-H Acetoxylation of 2-Pyridones2020

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

      Heterocycles

      Volume: 101 Issue: 1 Pages: 223-234

    • DOI

      10.3987/com-19-s(f)16

    • NAID

      40022128065

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis of gem-Difluoroalkenes by Copper-catalyzed Regioselective Hydrodefluorination of 1-Trifluoromethylalkenes2020

    • Author(s)
      Kojima Yuki、Takata Tatsuaki、Hirano Koji、Miura Masahiro
    • Journal Title

      Chemistry Letters

      Volume: 49 Issue: 6 Pages: 637-640

    • DOI

      10.1246/cl.200163

    • NAID

      130007852086

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Highly Stereoselective Synthesis of 1,2-Disubstituted Indanes by Pd-Catalyzed Heck/Suzuki Sequence of Diarylmethyl Carbonates2020

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

      Organic Letters

      Volume: 22 Issue: 8 Pages: 3190-3194

    • DOI

      10.1021/acs.orglett.0c00945

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Direct Synthesis of Dibenzophospholes from Biaryls by Double C-P Bond Formation via Phosphenium Dication Equivalents2020

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

      Organic Letters

      Volume: 22 Issue: 8 Pages: 3185-3189

    • DOI

      10.1021/acs.orglett.0c00944

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis of DPPP- and DPPPEN-Type Bidentate Ligands by Ring-Opening Diphosphination of Methylene- and Vinylcyclopropanes under Visible-Light-Promoted Photoredox Catalysis2020

    • Author(s)
      Yugo Kato, Nobutaka Otomura, Koji Hirano, Masahiro Miura
    • Journal Title

      The Journal of Organic Chemistry

      Volume: 85 Issue: 9 Pages: 5981-5994

    • DOI

      10.1021/acs.joc.0c00417

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Cu‐Catalyzed Reductive gem‐Difunctionalization of Terminal Alkynes via Hydrosilylation/Hydroamination Cascade: Concise Synthesis of α‐Aminosilanes2020

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

      Chemistry-A European Journal

      Volume: 26 Issue: 40 Pages: 8725-8728

    • DOI

      10.1002/chem.202001799

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Copper-Catalyzed Regioselective C-H Amination of Phenol Derivatives with Assistance of Phenanthroline-Based Bidentate Auxiliary2019

    • Author(s)
      Takamatsu Kazutaka、Hayashi Yoshihiro、Kawauchi Susumu、Hirano Koji、Miura Masahiro
    • Journal Title

      ACS Catalysis

      Volume: 9 Issue: 6 Pages: 5336-5344

    • DOI

      10.1021/acscatal.9b01145

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis of α-Trifluoromethylamines by Cu-Catalyzed Regio- and Enantioselective Hydroamination of 1-Trifluoromethylalkenes2019

    • Author(s)
      Takata Tatsuaki、Hirano Koji、Miura Masahiro
    • Journal Title

      Organic Letters

      Volume: 21 Issue: 11 Pages: 4284-4288

    • DOI

      10.1021/acs.orglett.9b01471

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Copper-Catalyzed Electrophilic Amination of gem-Diborylalkanes with Hydroxylamines Providing α-Aminoboronic Acid Derivatives2019

    • Author(s)
      Nishino Soshi、Hirano Koji、Miura Masahiro
    • Journal Title

      Organic Letters

      Volume: 21 Issue: 12 Pages: 4759-4762

    • DOI

      10.1021/acs.orglett.9b01640

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Diphosphination of ortho-quinone methide precursors with diphosphines2019

    • Author(s)
      Kato Yugo、Otomura Nobutaka、Hirano Koji、Miura Masahiro
    • Journal Title

      Tetrahedron Letters

      Volume: 60 Issue: 30 Pages: 2014-2017

    • DOI

      10.1016/j.tetlet.2019.06.055

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Copper‐Mediated Decarboxylative C-H Arylation of Phenol Derivatives with ortho‐Nitrobenzoic Acids Using Phenanthroline‐Based Bidentate Auxiliary2019

    • Author(s)
      Takamatsu Kazutaka、Hayashi Yoshihiro、Kawauchi Susumu、Hirano Koji、Miura Masahiro
    • Journal Title

      ChemistrySelect

      Volume: 4 Issue: 40 Pages: 11833-11838

    • DOI

      10.1002/slct.201902860

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Palladium‐Catalyzed Intramolecular Mizoroki‐Heck‐Type Reaction of Diarylmethyl Carbonates2019

    • Author(s)
      Matsude Akihiro、Hirano Koji、Miura Masahiro
    • Journal Title

      Advanced Synthesis & Catalysis

      Volume: 362 Issue: 3 Pages: 518-522

    • DOI

      10.1002/adsc.201901398

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis of Dibenzophospholes by Tf2O-Mediated Intramolecular Phospha-Friedel-Crafts-Type Reaction2019

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

      Organic Letters

      Volume: 21 Issue: 5 Pages: 1467-1470

    • DOI

      10.1021/acs.orglett.9b00219

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Journal Article] Synthesis of Seven‐Membered Benzolactones by Nickel‐Catalyzed C-H Coupling of Benzamides with Oxetanes2019

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

      Chemistry-A European Journal

      Volume: 印刷中 Issue: 40 Pages: 9400-9404

    • DOI

      10.1002/chem.201900543

    • Related Report
      2018 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Solvent‐Controlled Rh‐Catalyzed C6‐Selective C‐H Alkenylation and Alkylation of 2‐ Pyridones with Acrylates2019

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

      Asian Journal of Organic Chemistry

      Volume: 印刷中 Issue: 7 Pages: 1097-1101

    • DOI

      10.1002/ajoc.201900190

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Journal Article] Development of New C-N and C-P Bond Formations with Alkenes and Alkynes Based on Electrophilic Amination and Phosphination2018

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

      Journal of Synthetic Organic Chemistry, Japan

      Volume: 76 Issue: 11 Pages: 1206-1214

    • DOI

      10.5059/yukigoseikyokaishi.76.1206

    • NAID

      130007503332

    • ISSN
      0037-9980, 1883-6526
    • Year and Date
      2018-11-01
    • Related Report
      2018 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Palladium-Catalyzed Benzylic Phosphorylation of Diarylmethyl Carbonates2018

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

      Organic Letters

      Volume: 20 Issue: 12 Pages: 3553-3556

    • DOI

      10.1021/acs.orglett.8b01323

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Journal Article] Diphosphination of Arynes with Diphosphines2018

    • Author(s)
      Yuto Okugawa, Yoshihiro Hayashi, Susumu Kawauchi, Koji Hirano, Masahiro Miura
    • Journal Title

      Organic Letters

      Volume: 20 Issue: 12 Pages: 3670-3673

    • DOI

      10.1021/acs.orglett.8b01470

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Journal Article] Synthesis of α‐Aminophosphines by Copper‐Catalyzed Regioselective Hydroamination of Vinylphosphines2018

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

      Chemistry-A European Journal

      Volume: 24 Issue: 43 Pages: 10975-10978

    • DOI

      10.1002/chem.201802491

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Journal Article] Nickel‐Catalyzed Stereospecific C‐H Coupling of Benzamides with Epoxides2018

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

      Angewandte Chemie International Edition

      Volume: 57 Issue: 36 Pages: 11797-11801

    • DOI

      10.1002/anie.201807664

    • Related Report
      2018 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Phosphenium Cation Mediated Formal Cycloaddition Approach to Benzophospholes2018

    • Author(s)
      Kazutoshi Nishimura, Yuto Unoh, Koji Hirano, Masahiro Miura
    • Journal Title

      Chemistry-A European Journal

      Volume: 24 Issue: 50 Pages: 13089-13092

    • DOI

      10.1002/chem.201803225

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Journal Article] Diphosphination of 1,3-Dienes with Diphosphines under Visible-Light-Promoted Photoredox Catalysis2018

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

      Organic Letters

      Volume: 20 Issue: 24 Pages: 7965-7968

    • DOI

      10.1021/acs.orglett.8b03534

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Presentation] Copper-Catalyzed Regioselective C-H Amination of Phenol Derivatives with Assistance of Phenanthroline-Based Bidentate Auxiliary2019

    • Author(s)
      Koji Hirano
    • Organizer
      20th IUPAC International Symposium on Organometallic Chemistry Directed Towards Organic Synthesis (OMCOS20)
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Synthesis of Benzophospholes with Phosphenium Cations of Unique Reactivity2019

    • Author(s)
      Koji Hirano
    • Organizer
      27th International Society of Heterocyclic Chemistry Congress (27th ISHC)
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research
  • [Presentation] 極性転換が拓く新規炭素ーヘテロ元素結合形成2019

    • Author(s)
      平野 康次
    • Organizer
      日本薬学会第139年会シンポジウム「有機合成化学の若い力:今、ICHIBANアツい化学者たち」
    • Related Report
      2018 Research-status Report
    • Invited
  • [Presentation] Phosphination of Alkenes and Alkynes with Phosphinyl Radicals and Phosphenium Cations of Unique Reactivity2018

    • Author(s)
      Koji Hirano
    • Organizer
      International Symposium on Main Group Chemistry Directed towards Organic Synthesis (MACOS)
    • Related Report
      2018 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] Palladium-Catalyzed Asymmetric Benzylic Substitution of Secondary Benzyl Carbonates2018

    • Author(s)
      Koji Hirano
    • Organizer
      The 14th International Kyoto Conference on New Aspects of Organic Chemistry (IKCOC-14)
    • Related Report
      2018 Research-status Report
    • Int'l Joint Research
  • [Book] 直接的芳香族カップリング反応の設計と応用2019

    • Author(s)
      三浦雅博、平野康次
    • Total Pages
      212
    • Publisher
      シーエムシー出版
    • ISBN
      9784781314211
    • Related Report
      2019 Annual Research Report

URL: 

Published: 2018-07-25   Modified: 2021-02-19  

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