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Development of Novel Quaternary Phosphonium Salt Catalysts by the Use of Chiral Phosphine Library

Research Project

Project/Area Number 25870335
Research Category

Grant-in-Aid for Young Scientists (B)

Allocation TypeMulti-year Fund
Research Field Synthetic chemistry
Organic chemistry
Research InstitutionNagasaki University (2014)
Kyoto University (2013)

Principal Investigator

SHIRAKAWA Seiji  長崎大学, 水産・環境科学総合研究科(環境), 准教授 (60459865)

Project Period (FY) 2013-04-01 – 2015-03-31
Project Status Completed (Fiscal Year 2014)
Budget Amount *help
¥3,380,000 (Direct Cost: ¥2,600,000、Indirect Cost: ¥780,000)
Fiscal Year 2014: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
Fiscal Year 2013: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
Keywords第四級ホスホニウム塩 / 不斉合成 / 有機分子触媒 / 相間移動触媒 / 精密有機合成 / 環境調和型反応 / グリーンケミストリー / 触媒ライブラリ / キラル第四級ホスホニウム塩 / 二官能性触媒 / 触媒ライブラリー / アミド / 水素結合
Outline of Final Research Achievements

During last two decades, a variety of chiral quaternary ammonium salts have been developed as reliable catalysts for asymmetric phase-transfer reactions. On the other hand, only a few examples of chiral quaternary phosphonium salts have been reported, and hence the development of new effective chiral quaternary phosphonium salts is an important challenge in organocatalytic chemistry. Our approach for the discovery of effective chiral quaternary phosphonium salts relies on the use of commercially available chiral phosphine compounds as catalyst precursors. This approach allows facile construction of a catalyst library of chiral quaternary phosphonium salts. The optimized catalyst has successfully been applied to highly enantioselective conjugate additions under base-free neutral phase-transfer conditions with low catalyst loading. Based on the catalyst design, we have also developed new bifunctional phosphonium salts for highly enantioselective phase-transfer reactions.

Report

(3 results)
  • 2014 Annual Research Report   Final Research Report ( PDF )
  • 2013 Research-status Report
  • Research Products

    (13 results)

All 2015 2014 2013 Other

All Journal Article (6 results) (of which Peer Reviewed: 6 results,  Acknowledgement Compliant: 2 results) Presentation (4 results) (of which Invited: 1 results) Book (1 results) Remarks (2 results)

  • [Journal Article] Phase-transfer-catalyzed asymmetric desymmetrizations of cyclopentanones2015

    • Author(s)
      Seiji Shirakawa, Takashi Tokuda, S. B. Jennifer Kan, Keiji Maruoka
    • Journal Title

      Org. Chem. Front.

      Volume: 2 Issue: 4 Pages: 336-339

    • DOI

      10.1039/c4qo00339j

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Catalytic Asymmetric Synthesis of 3,3'-Diaryloxindoles as Triarylmethanes with a Chiral All-Carbon Quaternary Center : Phase-Transfer-Catalyzed SNAr Reaction2014

    • Author(s)
      S. Shirakawa, K. Koga, T. Tokuda, K. Yamamoto, K. Maruoka
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 53 Issue: 24 Pages: 6220-6223

    • DOI

      10.1002/anie.201403046

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Efficient asymmetric synthesis of spiro-2(3H)- furanones via phase-transfer-catalyzed alkynylation2014

    • Author(s)
      Xiangfei Wu, Seiji Shirakawa, Keiji Maruoka
    • Journal Title

      Org. Biomol. Chem.

      Volume: 12 Issue: 29 Pages: 5388-5392

    • DOI

      10.1039/c4ob00969j

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Efficient Approach for the Design of Effective Chiral Quaternary Phosphonium Salts in Asymmetric Conjugate Additions2013

    • Author(s)
      S. Shirakawa, A. Kasai, T. Tokuda, K. Maruoka
    • Journal Title

      Chemical Sciences

      Volume: 4 Issue: 5 Pages: 2248-2252

    • DOI

      10.1039/c3sc22130j

    • Related Report
      2013 Research-status Report
    • Peer Reviewed
  • [Journal Article] Design of Chiral Bifunctional Quaternary Phosphonium Bromide Catalysts Possessing an Amide Moiety2013

    • Author(s)
      Shirakawa, S.; Tokuda, T.; Kasai, A.; Maruoka, K.
    • Journal Title

      Org. Lett.

      Volume: 15 Issue: 13 Pages: 3350-3353

    • DOI

      10.1021/ol4013926

    • Related Report
      2013 Research-status Report
    • Peer Reviewed
  • [Journal Article] Recent Developments in Asymmetric Phase-Transfer Reactions2013

    • Author(s)
      Shirakawa, S.; Maruoka, K.
    • Journal Title

      Angew. Chem. Int. Ed.

      Volume: 52 Issue: 16 Pages: 4312-4348

    • DOI

      10.1002/anie.201206835

    • Related Report
      2013 Research-status Report
    • Peer Reviewed
  • [Presentation] Efficient Approach for the Design of Effective Chiral Quaternary Phosphonium Bromides in Asymmetric Reactions2014

    • Author(s)
      Seiji Shirakawa
    • Organizer
      2nd International Symposium on Integrated Science for Molecular Chirality in Biology and Chemistry
    • Place of Presentation
      Minamiaso, Kumamoto, Japan
    • Year and Date
      2014-11-30 – 2014-12-01
    • Related Report
      2014 Annual Research Report
    • Invited
  • [Presentation] 中性相間移動反応のための新規キラル第四級ホスホニウム塩触媒の創製2014

    • Author(s)
      白川誠司
    • Organizer
      第3回JACI/GSCシンポジウム
    • Place of Presentation
      東京国際フォ-ラム、東京
    • Year and Date
      2014-05-22 – 2014-05-23
    • Related Report
      2014 Annual Research Report
  • [Presentation] アミド部位を有する新規キラル二官能性第四級ホスホニウム塩触媒の創製とその応用2014

    • Author(s)
      徳田貴士、笠井淳如、白川誠司、丸岡啓二
    • Organizer
      日本化学会第94春季年会
    • Place of Presentation
      名古屋大学東山キャンパス
    • Related Report
      2013 Research-status Report
  • [Presentation] Design of Chiral Bifunctional Quaternary Phosphonium Bromide Catalysts Possessing Amide Moiety2013

    • Author(s)
      Tokuda, T.; Kasai, A.; Shirakawa, S.; Maruoka, K.
    • Organizer
      The 8th International Symposium on Intergrated Synthesis (ISIS-8)
    • Place of Presentation
      Todaiji Temple Cultural Center, Nara, Japan
    • Related Report
      2013 Research-status Report
  • [Book] Chiral Onium Salts In Comprehensive Enantioselective Organocatalysi2014

    • Author(s)
      Shirakawa, S.; Maruoka, K.
    • Publisher
      Wiley-VCH
    • Related Report
      2013 Research-status Report
  • [Remarks] 長崎大学 白川研究室 ホームページ

    • Related Report
      2014 Annual Research Report
  • [Remarks] http://seijishirakawa.wix.com/greenchemistry

    • Related Report
      2014 Annual Research Report

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Published: 2014-07-25   Modified: 2019-07-29  

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