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Design and development of hydrogen bond donor/phosphonium salt bifunctional catalysts

Research Project

Project/Area Number 17K14483
Research Category

Grant-in-Aid for Young Scientists (B)

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

Principal Investigator

Toda Yasunori  信州大学, 学術研究院工学系, 助教 (60758978)

Project Period (FY) 2017-04-01 – 2020-03-31
Project Status Completed (Fiscal Year 2019)
Budget Amount *help
¥4,420,000 (Direct Cost: ¥3,400,000、Indirect Cost: ¥1,020,000)
Fiscal Year 2019: ¥1,040,000 (Direct Cost: ¥800,000、Indirect Cost: ¥240,000)
Fiscal Year 2018: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Fiscal Year 2017: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000)
Keywords有機分子触媒 / 二官能性触媒 / ホスホニウム塩 / 環境調和 / 触媒反応 / 分子変換
Outline of Final Research Achievements

First, the mechanism of bifunctional tetraarylphosphonium salts-catalyzed [3+2] reactions of epoxides and carbon dioxide was investigated, revealing the substituent effect of the phosphonium salt catalysts. It was also found that the [3+2] reactions proceeded efficiently by a combined use of phosphonium ylides and metal salts as a catalyst. Next, the [3+2] reactions of epoxides with isocyanates were performed in the presence of a tetraarylphosphonium salt catalyst, where the corresponding oxazolidinones were obtained in good yields. In contrast, switched regioselectivity was observed in the case of glycidol, affording 4-hydroxymethyl oxazolidinones.

Academic Significance and Societal Importance of the Research Achievements

環境調和型物質合成プロセス開発の観点から、分子変換における効率の向上と選択性の獲得が求められており、化学反応を精密に制御し、高度な分子変換を実現する新規触媒の開発は重要な研究課題である。本研究では、反応を精密制御できる高活性な有機分子触媒として、新規テトラアリールホスホニウム塩触媒を開発し、これを用いる多様な分子変換技術の開発を行った。研究期間内に検討した反応は、工業的にあるいは医薬品合成などにおいて重要な生成物を与え、新規触媒の開発という学術的な観点だけでなく社会における合成化学的な観点からも大変意義深い。

Report

(4 results)
  • 2019 Annual Research Report   Final Research Report ( PDF )
  • 2018 Research-status Report
  • 2017 Research-status Report
  • Research Products

    (28 results)

All 2019 2018 2017 Other

All Journal Article (6 results) (of which Peer Reviewed: 6 results,  Open Access: 1 results) Presentation (16 results) (of which Int'l Joint Research: 2 results,  Invited: 2 results) Remarks (4 results) Patent(Industrial Property Rights) (2 results)

  • [Journal Article] 4-Hydroxymethyl-substituted oxazolidinone synthesis by tetraarylphosphonium salt-catalyzed reactions of glycidols with isocyanates2019

    • Author(s)
      Toda Yasunori、Tanaka Shoya、Gomyou Shuto、Kikuchi Ayaka、Suga Hiroyuki
    • Journal Title

      Chemical Communications

      Volume: 55 Issue: 41 Pages: 5761-5764

    • DOI

      10.1039/c9cc01983a

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Visible-light-triggered Catalytic Halohydrin Synthesis from Epoxides and Trichloroacetonitrile by Copper and Iron Salts2019

    • Author(s)
      Toda Yasunori、Tanaka Katsumi、Matsuda Riki、Suga Hiroyuki
    • Journal Title

      Chemistry Letters

      Volume: 48 Issue: 12 Pages: 1469-1471

    • DOI

      10.1246/cl.190679

    • NAID

      130007757569

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Methoxy groups increase reactivity of bifunctional tetraarylphosphonium salt catalysts for carbon dioxide fixation: A mechanistic study2019

    • Author(s)
      Yasunori Toda, Yutaka Komiyama, Hiroyoshi Esaki, Kazuaki Fukushima, Hiroyuki Suga
    • Journal Title

      J. Org. Chem.

      Volume: 84 Issue: 23 Pages: 15578-15589

    • DOI

      10.1021/acs.joc.9b02581

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Use of trichloroacetonitrile as a hydrogen chloride generator for ring-opening reactions of aziridines2019

    • Author(s)
      Toda Yasunori、Matsuda Riki、Gomyou Shuto、Suga Hiroyuki
    • Journal Title

      Organic & Biomolecular Chemistry

      Volume: 17 Issue: 15 Pages: 3825-3829

    • DOI

      10.1039/c9ob00602h

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Journal Article] A Phosphonium Ylide as an Ionic Nucleophilic Catalyst for Primary Hydroxyl Group Selective Acylation of Diols2017

    • Author(s)
      Yasunori Toda, Tomoyuki Sakamoto, Yutaka Komiyama, Ayaka Kikuchi, Hiroyuki Suga
    • Journal Title

      ACS Catalysis

      Volume: 7 Issue: 9 Pages: 6150-6154

    • DOI

      10.1021/acscatal.7b02281

    • Related Report
      2017 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Tetraarylphosphonium Salt-Catalyzed Synthesis of Oxazolidinones from Isocyanates and Epoxides2017

    • Author(s)
      Yasunori Toda, Shuto Gomyou, Shoya Tanaka, Yutaka Komiyama, Ayaka Kikuchi, Hiroyuki Suga
    • Journal Title

      Organic Letters

      Volume: 19 Issue: 21 Pages: 5786-5789

    • DOI

      10.1021/acs.orglett.7b02722

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Presentation] ホスホニウムイリドと金属塩を用いる二酸化炭素固定化反応の開発2019

    • Author(s)
      橋本耕佑, 森陽子, 戸田泰徳, 菅博幸
    • Organizer
      第36回有機合成化学セミナー
    • Related Report
      2019 Annual Research Report
  • [Presentation] 金属触媒および可視光照射下におけるエポキシドからのハロヒドリン合成2019

    • Author(s)
      田中克, 松田倫宜, 戸田泰徳, 菅博幸
    • Organizer
      第50回中部化学関係協会支部連合秋季大会
    • Related Report
      2019 Annual Research Report
  • [Presentation] ホスホニウムイリドと金属塩を用いる常圧下での二酸化炭素固定化反応2019

    • Author(s)
      橋本耕佑, 森陽子, 戸田泰徳, 菅博幸
    • Organizer
      第50回中部化学関係協会支部連合秋季大会
    • Related Report
      2019 Annual Research Report
  • [Presentation] トリクロロアセトニトリルを用いる光照射下でのアジリジン開環反応2019

    • Author(s)
      松田倫宜, 五明秀斗, 戸田泰徳, 菅博幸
    • Organizer
      日本化学会第99春季年会
    • Related Report
      2018 Research-status Report
  • [Presentation] テトラアリールホスホニウム塩触媒を用いるグリシドールとイソシアネートからのオキサゾリジノン合成2019

    • Author(s)
      戸田泰徳, 田中祥也, 五明秀斗, 菅博幸
    • Organizer
      日本化学会第99春季年会
    • Related Report
      2018 Research-status Report
  • [Presentation] 二官能性テトラアリールホスホニウム塩触媒の開発2018

    • Author(s)
      戸田泰徳
    • Organizer
      平成30年度有機合成化学協会東海支部若手研究者のためのセミナー
    • Related Report
      2018 Research-status Report
    • Invited
  • [Presentation] 二官能性ホスホニウム塩触媒による二酸化炭素とエポキシドのカップリング反応の反応機構解析2018

    • Author(s)
      戸田泰徳, 小見山裕崇, 江嵜啓祥, 福島和明, 菅博幸
    • Organizer
      第48回複素環化学討論会
    • Related Report
      2018 Research-status Report
  • [Presentation] トリクロロアセトニトリルを用いる光照射下でのアジリジン開環反応2018

    • Author(s)
      松田倫宜, 五明秀斗, 戸田泰徳, 菅博幸
    • Organizer
      第49回中部化学関係協会支部連合秋季大会
    • Related Report
      2018 Research-status Report
  • [Presentation] Development and Mechanistic Study of Bifunctional Phosphonium Salt-Catalyzed Coupling Reactions of Carbon Dioxide with Epoxides2018

    • Author(s)
      戸田泰徳,小見山裕崇,江嵜啓祥,福島和明,菅博幸
    • Organizer
      日本化学会第98春季年会
    • Related Report
      2017 Research-status Report
  • [Presentation] テトラアリールホスホニウム骨格をベースとした有機分子触媒の開発2017

    • Author(s)
      戸田泰徳
    • Organizer
      平成29年度有機合成化学協会東海支部 若手研究者のためのセミナー
    • Related Report
      2017 Research-status Report
    • Invited
  • [Presentation] Tetraarylphosphonium Salt-Catalyzed Carbon Dioxide Fixation2017

    • Author(s)
      小見山裕崇,戸田泰徳,菅博幸
    • Organizer
      HALCHEM VIII
    • Related Report
      2017 Research-status Report
    • Int'l Joint Research
  • [Presentation] Tetraarylphosphonium Salt-Catalyzed Synthesis of Oxazolidinones from Isocyanates and Epoxides2017

    • Author(s)
      五明秀斗,田中祥也,小見山裕崇,戸田泰徳,菅博幸
    • Organizer
      HALCHEM VIII
    • Related Report
      2017 Research-status Report
    • Int'l Joint Research
  • [Presentation] 二官能性テトラアリールホスホニウム塩触媒による常圧下での二酸化炭素固定反応2017

    • Author(s)
      小見山裕崇,江嵜啓祥,福島和明,戸田泰徳,菅博幸
    • Organizer
      第47回複素環化学討論会
    • Related Report
      2017 Research-status Report
  • [Presentation] 二官能性テトラアリールホスホニウム塩触媒を用いるオキサゾリジノン合成2017

    • Author(s)
      田中祥也,五明秀斗,小見山裕崇,戸田泰徳,菅博幸
    • Organizer
      第47回複素環化学討論会
    • Related Report
      2017 Research-status Report
  • [Presentation] 置換基修飾した二官能性テトラアリールホスホニウム塩触媒による二酸化炭素固定化反応の効率化2017

    • Author(s)
      小見山裕崇,江嵜啓祥,福島和明,戸田泰徳,菅博幸
    • Organizer
      第48回中部化学関係学教会支部連合秋季大会
    • Related Report
      2017 Research-status Report
  • [Presentation] 新規イオン性求核触媒の開発と第一級アルコールの選択的アシル化反応における触媒能評価2017

    • Author(s)
      坂本智行,小見山裕崇,戸田泰徳,菅博幸
    • Organizer
      第48回中部化学関係学教会支部連合秋季大会
    • Related Report
      2017 Research-status Report
  • [Remarks] 研究室ホームページ

    • URL

      http://www.shinshu-u.ac.jp/faculty/engineering/chair/chem002/index.html

    • Related Report
      2019 Annual Research Report 2018 Research-status Report 2017 Research-status Report
  • [Remarks] 信州大学トピックス(1)

    • URL

      https://www.shinshu-u.ac.jp/topics/2018/08/post-70.html

    • Related Report
      2018 Research-status Report
  • [Remarks] 信州大学トピックス(2)

    • URL

      https://www.shinshu-u.ac.jp/topics/2018/09/chemical-science-poster-prize.html

    • Related Report
      2018 Research-status Report
  • [Remarks] 信州大学トピックス

    • URL

      http://www.shinshu-u.ac.jp/topics/2017/08/acs-editors-choice.html

    • Related Report
      2017 Research-status Report
  • [Patent(Industrial Property Rights)] ルイス酸・ハロゲン化物イオン複合型触媒およびルイス酸・ハロゲン化物 イオン複合型触媒による二酸化炭素固定化方法2019

    • Inventor(s)
      戸田泰徳、菅博幸、橋本耕佑
    • Industrial Property Rights Holder
      信州大学
    • Industrial Property Rights Type
      特許
    • Industrial Property Number
      2019-094967
    • Filing Date
      2019
    • Related Report
      2019 Annual Research Report
  • [Patent(Industrial Property Rights)] イオン性求核触媒およびこれを用いたアシル化方法2017

    • Inventor(s)
      戸田泰徳,菅博幸,坂本智行,小見山裕崇
    • Industrial Property Rights Holder
      信州大学
    • Industrial Property Rights Type
      特許
    • Industrial Property Number
      2017-161926
    • Filing Date
      2017
    • Related Report
      2017 Research-status Report

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Published: 2017-04-28   Modified: 2021-02-19  

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