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New Possibilities of Sulfonium Salts in Organic Synthesis

Research Project

Project/Area Number 16K05780
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Research Field Synthetic chemistry
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) 2016-04-01 – 2019-03-31
Project Status Completed (Fiscal Year 2018)
Budget Amount *help
¥4,940,000 (Direct Cost: ¥3,800,000、Indirect Cost: ¥1,140,000)
Fiscal Year 2018: ¥1,040,000 (Direct Cost: ¥800,000、Indirect Cost: ¥240,000)
Fiscal Year 2017: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
Fiscal Year 2016: ¥2,600,000 (Direct Cost: ¥2,000,000、Indirect Cost: ¥600,000)
Keywords有機分子触媒 / 不斉合成 / 触媒設計 / 水素結合 / 硫黄触媒 / オニウム塩 / スルホニウム塩 / グリーンケミストリー / 相間移動触媒 / 水素結合供与型触媒
Outline of Final Research Achievements

Despite the wide synthetic utility of onium salts as reagents and catalysts, the catalytic ability of tertiary sulfonium salts has not yet been demonstrated well in organic synthesis. To create new possibilities for sulfonium salts as catalysts, we focused on the hydrogen-bonding abilities of α hydrogens on alkylsulfonium salts when we reported the use of new tetraalkylammonium salts as hydrogen-bonding catalysts. Based on the design of the ammonium salts, we focused on simple cyclic trialkylsulfonium salts. The catalytic ability of sulfonium salts was superior to that of the related ammonium salts. We have also demonstrated that chiral tertiary sulfonium salts can promote asymmetric reactions. Binaphthyl-modified bifunctional sulfonium salts were efficient catalysts for the asymmetric reactions under base-free phase-transfer conditions. As far as could be ascertained, this is the first example of a highly enantioselective reaction catalyzed by chiral sulfonium salts.

Academic Significance and Societal Importance of the Research Achievements

これまで未開拓であった、第三級スルホニウム塩の触媒としての機能を引き出すことに成功し、有機硫黄化学の新たな可能性を示した。本研究は、地球上に豊富に存在する硫黄元素の特性を引き出した研究であり、元素戦略の観点から重要な研究である。また、環境に調和した新たな精密有機合成手法を確立しており、有用化合物のグリーンケミストリーに根ざした実用的合成へ繋がると期待される。

Report

(4 results)
  • 2018 Annual Research Report   Final Research Report ( PDF )
  • 2017 Research-status Report
  • 2016 Research-status Report
  • Research Products

    (22 results)

All 2019 2018 2017 2016 Other

All Journal Article (6 results) (of which Peer Reviewed: 6 results,  Acknowledgement Compliant: 2 results) Presentation (12 results) (of which Int'l Joint Research: 2 results,  Invited: 8 results) Book (1 results) Remarks (3 results)

  • [Journal Article] Design of Chiral Bifunctional Dialkyl Sulfide Catalysts for Regio-, Diastereo-, and Enantioselective Bromolactonization2018

    • Author(s)
      Nishiyori Ryuichi、Tsuchihashi Ayano、Mochizuki Ayaka、Kaneko Kazuma、Yamanaka Masahiro、Shirakawa Seiji
    • Journal Title

      Chem. Eur. J.

      Volume: 24 Issue: 63 Pages: 16747-16752

    • DOI

      10.1002/chem.201803703

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] KI-Tetraethylene Glycol Complex as an Effective Catalyst for the Synthesis of Cyclic Thiocarbonates from Epoxides and CS22018

    • Author(s)
      Megumi Okada, Ryuichi Nishiyori, Shiho Kaneko, Kazunobu Igawa, Seiji Shirakawa
    • Journal Title

      Eur. J. Org. Chem.

      Volume: (17) Issue: 17 Pages: 2022-2027

    • DOI

      10.1002/ejoc.201800284

    • NAID

      120006988081

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Hydrogen-bonding catalysis of sulfonium salts2017

    • Author(s)
      Shiho Kaneko, Yusuke Kumatabara, Shoichi Shimizu, Keiji Maruoka, Seiji Shirakawa
    • Journal Title

      Chem. Commun.

      Volume: 53 Issue: 1 Pages: 119-122

    • DOI

      10.1039/c6cc08411g

    • NAID

      120006987581

    • Related Report
      2017 Research-status Report 2016 Research-status Report
    • Peer Reviewed
  • [Journal Article] Chiral Tertiary Sulfonium Salts as Effective Catalysts for Asymmetric Base-Free Neutral Phase-Transfer Reactions2017

    • Author(s)
      Shiyao Liu, Keiji Maruoka, Seiji Shirakawa
    • Journal Title

      Angew. Chem. Int. Ed.

      Volume: 56 Issue: 17 Pages: 4819-4823

    • DOI

      10.1002/anie.201612328

    • NAID

      120006987514

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] Hydrogen-Bonding Catalysis of Tetraalkylammonium Salts in an Aza-Diels Alder Reaction2016

    • Author(s)
      Kumatabara, Y.; Kaneko, S.; Nakata, S.; Shirakawa, S.; Maruoka, K.
    • Journal Title

      Chem. Asian J.

      Volume: 11 Issue: 15 Pages: 2126-2129

    • DOI

      10.1002/asia.201600781

    • Related Report
      2016 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Design of bifunctional quaternary phosphonium salt catalysts for CO2 fixation reaction with epoxides under mild conditions2016

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

      Green Chem.

      Volume: 18 Issue: 17 Pages: 4611-4615

    • DOI

      10.1039/c6gc01630h

    • Related Report
      2016 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Presentation] Design of Chiral Organosulfur Catalysts2019

    • Author(s)
      白川 誠司
    • Organizer
      日本化学会第99春季年会
    • Related Report
      2018 Annual Research Report
    • Invited
  • [Presentation] Design of Organo-sulfur Catalysts2018

    • Author(s)
      Seiji Shirakawa
    • Organizer
      9th Joint CSJ RSC Symposium: Designing Molecular Function at the Nano-Scale: Catalysis, Materials and Supramolecular Chemistry
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] 硫黄の特徴を生かした触媒開発2018

    • Author(s)
      白川 誠司
    • Organizer
      第30回若手研究者のためのセミナー
    • Related Report
      2018 Annual Research Report
    • Invited
  • [Presentation] 新たな有機硫黄触媒の開発2018

    • Author(s)
      白川 誠司
    • Organizer
      第79回超分子創製化学セミナー
    • Related Report
      2018 Annual Research Report
    • Invited
  • [Presentation] Catalysis of Trialkylsulfonium Salts2018

    • Author(s)
      Seiji Shirakawa
    • Organizer
      日本化学会第98春季年会
    • Related Report
      2017 Research-status Report
    • Invited
  • [Presentation] 水素結合供与型触媒としてのスルホニウム塩の利用2017

    • Author(s)
      金子 詩歩・丸岡 啓二・白川 誠司
    • Organizer
      日本化学会第97春季年会
    • Place of Presentation
      慶應義塾大学 日吉キャンパス (神奈川県横浜市)
    • Year and Date
      2017-03-16
    • Related Report
      2016 Research-status Report
  • [Presentation] 第四級アンモニウム塩を水素結合供与型触媒として用いたアザデ ィールス・アルダー反応2017

    • Author(s)
      熊田原 佑亮・丸岡 啓二・白川 誠司
    • Organizer
      日本化学会第97春季年会
    • Place of Presentation
      慶應義塾大学 日吉キャンパス (神奈川県横浜市)
    • Year and Date
      2017-03-16
    • Related Report
      2016 Research-status Report
  • [Presentation] 二酸化炭素固定化反応のための二官能性ホスホニウム塩触媒の 開発2017

    • Author(s)
      劉 詩堯・丸岡 啓二・白川 誠司
    • Organizer
      日本化学会第97春季年会
    • Place of Presentation
      慶應義塾大学 日吉キャンパス (神奈川県横浜市)
    • Year and Date
      2017-03-16
    • Related Report
      2016 Research-status Report
  • [Presentation] 新規キラル第三級スルホニウム塩触媒の創製と中性相間移動反応への適用2017

    • Author(s)
      劉 詩堯、丸岡 啓二、白川 誠司
    • Organizer
      第27回万有福岡シンポジウム
    • Related Report
      2017 Research-status Report
  • [Presentation] The New Dimension of Alkyl-onium Salt Catalysts2017

    • Author(s)
      Seiji Shirakawa
    • Organizer
      The 7th Sino-Japanese Symposium on Organic Chemistry for Young Scientists
    • Related Report
      2017 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] オニウム塩触媒のちょっと違う使い方2016

    • Author(s)
      白川 誠司
    • Organizer
      九州大学「先端有機化学講演会」
    • Place of Presentation
      九州大学先導物質化学研究所 筑紫キャンパス (福岡県春日市)
    • Year and Date
      2016-12-05
    • Related Report
      2016 Research-status Report
    • Invited
  • [Presentation] オニウム塩触媒の新たな可能性の探索2016

    • Author(s)
      白川 誠司
    • 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 山手キャンパス (愛知県岡崎市)
    • Year and Date
      2016-11-10
    • Related Report
      2016 Research-status Report
    • Invited
  • [Book] Designed Molecular Space in Material Science and Catalysis2018

    • Author(s)
      Seiji Shirakawa Ed. (Hiromitsu Maeda, Tomoki Ogoshi, Seiji Shirakawa, Takashi Murase, Yoshihiro Sohtome, Takumi Furuta, Naoya Kumagai, Yuuya Nagata, Yoshinori Takashima, Tatsushi Imahori, Ryosuke Miyake)
    • Total Pages
      262
    • Publisher
      Springer
    • ISBN
      9789811312557
    • Related Report
      2018 Annual Research Report
  • [Remarks] 長崎大学 白川研究室 ホームページ

    • URL

      http://seijishirakawa.wixsite.com/greenchemistry

    • Related Report
      2018 Annual Research Report 2017 Research-status Report
  • [Remarks] 長崎大学 白川研究室HP

    • URL

      http://seijishirakawa.wixsite.com/greenchemistry

    • Related Report
      2016 Research-status Report
  • [Remarks] 長崎大学 白川誠司 研究者データベース

    • URL

      http://research.jimu.nagasaki-u.ac.jp/IST?ISTActId=FINDJPDetail&ISTKidoKbn=&ISTErrorChkKbn=&ISTFormSetKbn=&ISTTokenChkKbn=&userId=100000992

    • Related Report
      2016 Research-status Report

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Published: 2016-04-21   Modified: 2020-03-30  

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