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Design of Chiral Sulfide Catalysts for Direct Precise Transformations of Alkenes

Research Project

Project/Area Number 19K05480
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Review Section Basic Section 33020:Synthetic organic chemistry-related
Research InstitutionNagasaki University

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) 2019-04-01 – 2023-03-31
Project Status Completed (Fiscal Year 2022)
Budget Amount *help
¥4,420,000 (Direct Cost: ¥3,400,000、Indirect Cost: ¥1,020,000)
Fiscal Year 2021: ¥910,000 (Direct Cost: ¥700,000、Indirect Cost: ¥210,000)
Fiscal Year 2020: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
Fiscal Year 2019: ¥2,210,000 (Direct Cost: ¥1,700,000、Indirect Cost: ¥510,000)
Keywords不斉合成 / 有機分子触媒 / グリーンケミストリー / 複素環式化合物 / ハロゲン化反応 / 有機合成化学 / プラネタリーヘルス / 有機触媒 / ラクトン / エステル / カルボン酸 / 精密有機合成 / 環境調和型触媒 / カルコゲン / アミノ化 / ハロゲン化 / 二官能性触媒 / 触媒設計 / アルケン / スルフィド触媒 / 複素環化合物 / 分子認識 / 分子デザイン
Outline of Research at the Start

医薬品などの効率的合成法の確立を目指し、石油精製により得られる単純なアルケンへの高選択的官能基導入法の開発を行う。硫黄元素の特性に着目した、新奇二官能性キラルスルフィド触媒を設計し、これを用いた環境調和型反応開発を行う。本手法が確立できれば、医薬品や機能性材料の製造工程の大幅な簡略化に繋がることから、化学工業の様々な場面で利用される手法になると期待している。

Outline of Final Research Achievements

Catalytic asymmetric reactions with unactivated alkene substrates are still limited despite the reactions create straightforward methods for the preparation of important chiral molecules in enantioenriched forms. Thus, developments of new catalytic asymmetric strategies for the enantioselective transformations of unactivated alkenes are highly desired. In this project, we have developed new chiral bifunctional sulfide catalysts to achieve the catalytic asymmetric transformations of unactivated alkenes. The newly developed chiral bifunctional sulfides promoted enantioselective bromocyclization reactions to provide important chiral heterocyclic products in optically active forms.

Academic Significance and Societal Importance of the Research Achievements

本研究では、独自の概念に基づいた触媒設計により、既存の触媒では達成困難な新たな立体選択的反応の開発を実現しており、学術的意義のある研究成果である。また、本触媒手法を活用することで、医薬品開発のシーズとなる化合物群のライブラリー構築を実現しており、生命科学へも貢献しうる研究内容である。

Report

(5 results)
  • 2022 Annual Research Report   Final Research Report ( PDF )
  • 2021 Research-status Report
  • 2020 Research-status Report
  • 2019 Research-status Report
  • Research Products

    (31 results)

All 2023 2022 2021 2020 2019 Other

All Int'l Joint Research (3 results) Journal Article (10 results) (of which Int'l Joint Research: 3 results,  Peer Reviewed: 10 results,  Open Access: 1 results) Presentation (15 results) (of which Int'l Joint Research: 4 results,  Invited: 5 results) Book (1 results) Remarks (2 results)

  • [Int'l Joint Research] University of Southampton(英国)

    • Related Report
      2021 Research-status Report
  • [Int'l Joint Research] Tanta University(エジプト)

    • Related Report
      2021 Research-status Report
  • [Int'l Joint Research] University of Southampton(英国)

    • Related Report
      2019 Research-status Report
  • [Journal Article] Asymmetric Synthesis of α-Spiro-γ-lactones and α-Substituted γ-Lactones via Chiral Bifunctional Sulfide-Catalyzed Bromolactonizations2023

    • Author(s)
      T. Mori, K. Abe, S. Shirakawa
    • Journal Title

      J. Org. Chem.

      Volume: 88 Issue: 12 Pages: 7830-7838

    • DOI

      10.1021/acs.joc.2c02283

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Chiral Bifunctional Selenide Catalysts for Asymmetric Iodolactonizations2022

    • Author(s)
      Nishiyori Ryuichi、Okuno Ken、Chan Bun、Shirakawa Seiji
    • Journal Title

      Chemical and Pharmaceutical Bulletin

      Volume: 70 Issue: 9 Pages: 599-604

    • DOI

      10.1248/cpb.c22-00049

    • ISSN
      0009-2363, 1347-5223
    • Year and Date
      2022-09-01
    • Related Report
      2022 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Efficient methods for the synthesis of chiral 2‐oxazolidinones as pharmaceutical building blocks2022

    • Author(s)
      Okuno Ken、Nishiyori Ryuichi、Abe Koki、Mori Taiki、Shirakawa Seiji
    • Journal Title

      Chirality

      Volume: 34 Issue: 7 Pages: 915-924

    • DOI

      10.1002/chir.23452

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Efficient Asymmetric Syntheses of α-Quaternary Lactones and Esters through Chiral Bifunctional Sulfide-Catalyzed Desymmetrizing Bromolactonization of α,α-Diallyl Carboxylic Acids2021

    • Author(s)
      Mana Hiraki, Ken Okuno, Ryuichi Nishiyori, Ahmed A. Noser, Seiji Shirakawa
    • Journal Title

      Chemical Communications

      Volume: 57 Issue: 83 Pages: 10907-10910

    • DOI

      10.1039/d1cc03874e

    • Related Report
      2021 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Chiral Bifunctional Sulfide‐Catalyzed Highly Enantioselective Bromolactonizations of 4‐Pentenoic Acids2021

    • Author(s)
      Ryuichi Nishiyori, Megumi Okada, John R. J. Maynard, Seiji Shirakawa
    • Journal Title

      Asian Journal of Organic Chemistry

      Volume: 10 Issue: 6 Pages: 1444-1448

    • DOI

      10.1002/ajoc.202000644

    • Related Report
      2021 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Asymmetric Catalysis of Chiral Bifunctional Selenides and Selenonium Salts Bearing a Urea Group2021

    • Author(s)
      Ken Okuno, Takumi Nakamura, Seiji Shirakawa
    • Journal Title

      Asian Journal of Organic Chemistry

      Volume: 10 Issue: 3 Pages: 655-659

    • DOI

      10.1002/ajoc.202100001

    • Related Report
      2020 Research-status Report
    • Peer Reviewed
  • [Journal Article] Chiral bifunctional sulfide-catalyzed asymmetric bromoaminocyclizations2020

    • Author(s)
      Nakamura, T.; Okuno, K.; Kaneko, K.; Yamanaka, M.; Shirakawa, S.
    • Journal Title

      Org. Biomol. Chem.

      Volume: 18 Issue: 17 Pages: 3367-3373

    • DOI

      10.1039/d0ob00459f

    • NAID

      120006988200

    • Related Report
      2020 Research-status Report
    • Peer Reviewed
  • [Journal Article] Chiral Bifunctional Selenide Catalysts for Asymmetric Bromolactonization2020

    • Author(s)
      Ryuichi Nishiyori, John R. J. Maynard, Seiji Shirakawa
    • Journal Title

      Asian Journal of Organic Chemistry

      Volume: 9 Issue: 2 Pages: 192-196

    • DOI

      10.1002/ajoc.201900688

    • Related Report
      2019 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] BINOL-derived bifunctional sulfide catalysts for asymmetric synthesis of 3,3-disubstituted phthalides via bromolactonization2019

    • Author(s)
      Megumi Okada, Kazuma Kaneko, Masahiro Yamanaka, Seiji Shirakawa
    • Journal Title

      Organic & Biomolecular Chemistry

      Volume: 17 Issue: 15 Pages: 3747-3751

    • DOI

      10.1039/c9ob00417c

    • NAID

      120006987740

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] Catalyst-Controlled Regio- and Stereoselective Bromolactonization with Chiral Bifunctional Sulfides2019

    • Author(s)
      Ayano Tsuchihashi, Seiji Shirakawa
    • Journal Title

      Synlett

      Volume: 30 Issue: 14 Pages: 1662-1666

    • DOI

      10.1055/s-0037-1610716

    • NAID

      120006988430

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Presentation] Design of Chiral Bifunctional Sulfide Catalysts for Asymmetric Halocyclizations2022

    • Author(s)
      Seiji Shirakawa
    • Organizer
      11th Singapore International Chemical Conference (SICC-11)
    • Related Report
      2022 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] 独自に設計したキラルスルフィド触媒の創製2022

    • Author(s)
      白川 誠司
    • Organizer
      第90回 触媒化学融合研究センター講演会
    • Related Report
      2022 Annual Research Report
    • Invited
  • [Presentation] キラル二官能性スルフィド触媒を用いたα-アリルカルボン酸の不斉ブロモラクトン化反応2022

    • Author(s)
      森太紀, 白川誠司
    • Organizer
      第38回 有機合成化学セミナー
    • Related Report
      2022 Annual Research Report
  • [Presentation] キラル二官能性スルフィド触媒を用いたα位に不斉四級炭素をもつカルボン酸の速度論的光学分割2022

    • Author(s)
      奥野 研, 平木 麻奈, Bun Chan, 白川 誠司
    • Organizer
      第38回 有機合成化学セミナー
    • Related Report
      2022 Annual Research Report
  • [Presentation] Kinetic Resolution of α-Quaternary Carboxylic Acids via Chiral Bifunctional Sulfide-Catalyzed Bromolactonization2022

    • Author(s)
      Seiji Shirakawa
    • Organizer
      The 15th International Conference on Cutting-Edge Organic Chemistry in Asia (ICCEOCA-15)
    • Related Report
      2022 Annual Research Report
    • Int'l Joint Research
  • [Presentation] 実用的二酸化炭素変換反応の実現に向けた二官能性有機分子触媒の設計と展開2022

    • Author(s)
      白川誠司
    • Organizer
      第25回農薬相模セミナー
    • Related Report
      2021 Research-status Report
    • Invited
  • [Presentation] キラル二官能性スルフィド触媒を用いた高エナンチオ選択的ブロモラクトン化反応によるγ-ブチロラクトン合成2021

    • Author(s)
      西依隆一、白川誠司
    • Organizer
      第31回 万有福岡シンポジウム
    • Related Report
      2021 Research-status Report
  • [Presentation] キラル二官能性スルフィド触媒を用いたブロモラクトン化反応による不斉四級炭素を有するラクトンおよびエステルの高立体選択的合成2021

    • Author(s)
      平木麻奈、奥野研、西依隆一、白川誠司
    • Organizer
      第14 回有機触媒シンポジウム
    • Related Report
      2021 Research-status Report
  • [Presentation] キラル二官能性スルフィド触媒を用いたブロモアミノ化反応によるエナンチオ選択的インドリン合成2020

    • Author(s)
      中村 巧, 奥野 研, 白川 誠司
    • Organizer
      第30回記念 万有福岡シンポジウム
    • Related Report
      2020 Research-status Report
  • [Presentation] ウレア型キラル二官能性スルフィド触媒による高エナンチオ選択的ブロモアミノ化反応2020

    • Author(s)
      中村 巧, 奥野 研, 白川 誠司
    • Organizer
      第117回 有機合成シンポジウム
    • Related Report
      2020 Research-status Report
  • [Presentation] キラル二官能性セレニド触媒の創製と不斉ブロモラクトン化反応への適用2020

    • Author(s)
      西依隆一, 白川誠司
    • Organizer
      第117回 有機合成シンポジウム
    • Related Report
      2020 Research-status Report
  • [Presentation] Design of Chiral Bifunctional Organosulfur Catalysts2019

    • Author(s)
      Seiji Shirakawa
    • Organizer
      The 18th Asian Chemical Congress
    • Related Report
      2019 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] 環境調和型有機合成反応の開発を指向した有機分子触媒の設計2019

    • Author(s)
      白川 誠司
    • Organizer
      第124回触媒討論会
    • Related Report
      2019 Research-status Report
    • Invited
  • [Presentation] Design of Chiral Bifunctional Sulfide Catalysts for Asymmetric Bromolactonizations2019

    • Author(s)
      Seiji Shirakawa, Ayano Tsuchihashi, Takumi Nakamura, Ryuichi Nishiyori, Megumi Okada
    • Organizer
      27th International Society of Heterocyclic Chemistry Congress
    • Related Report
      2019 Research-status Report
    • Int'l Joint Research
  • [Presentation] キラル二官能性スルフィド触媒によるスチルベン型カルボン酸の位置および立体選択的ブロモラクトン化反応2019

    • Author(s)
      土橋 彩乃, 白川 誠司
    • Organizer
      第29回万有福岡シンポジウム
    • Related Report
      2019 Research-status Report
  • [Book] Quaternary Ammonium, Phosphonium, and Tertiary Sulfonium Salts as Hydrogen-Bonding Catalysts (in Anion-Binding Catalysis, Garcia Mancheno, Olga Ed)2022

    • Author(s)
      Seiji Shirakawa
    • Total Pages
      416
    • Publisher
      Wiley-VCH
    • ISBN
      9783527348572
    • Related Report
      2021 Research-status Report
  • [Remarks] 長崎大学グリーンケミストリー(白川)研究室

    • URL

      https://seijishirakawa.wixsite.com/greenchemistry

    • Related Report
      2022 Annual Research Report
  • [Remarks] 長崎大学 白川研究室 ホームページ

    • URL

      https://seijishirakawa.wixsite.com/greenchemistry

    • Related Report
      2021 Research-status Report 2020 Research-status Report 2019 Research-status Report

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Published: 2019-04-18   Modified: 2024-01-30  

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