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Design and development of the reactions using organocatalyst by computational screening

Research Project

Project/Area Number 17KT0096
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section特設分野
Research Field Transition State Control
Research InstitutionShinshu University

Principal Investigator

Suga Hiroyuki  信州大学, 学術研究院工学系, 教授 (60211299)

Co-Investigator(Kenkyū-buntansha) 戸田 泰徳  信州大学, 学術研究院工学系, 助教 (60758978)
Project Period (FY) 2017-07-18 – 2020-03-31
Project Status Completed (Fiscal Year 2019)
Budget Amount *help
¥4,550,000 (Direct Cost: ¥3,500,000、Indirect Cost: ¥1,050,000)
Fiscal Year 2019: ¥1,170,000 (Direct Cost: ¥900,000、Indirect Cost: ¥270,000)
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不斉付加環化 / 二酸化炭素固定化 / 有機触媒 / 計算化学 / 遷移状態 / 反応機構 / 環状ニトロン / ヒドロキシスチレン / ニトリルオキシド / ニトロン / アゾメチンイミン / フロンティア軌道理論 / 有機化学 / 有機分子触媒
Outline of Final Research Achievements

The transition state with anti-open type conformation of a chiral amine-urea catalyst was found to be favored for highly enantioselective cycloaddition reactions between aromatic nitrile oxides and 2-hydroxystyrene derivatives by DFT calculations. This methodology could be applicable to cycloadditions of in situ generated aliphatic nitrile oxides, cyclic nitrone, C,N-diaryl nitrone, and N,N’-cyclic azomethine imines with 2-hydroxy-3-methoxystyrene in the presence of a chiral amine-urea derived from quinine with high to good enantioselectivities.
In the carbon dioxide fixation using epoxides catalyzed by tetraarylphosphonium salts (TAPS) as an organocatalyst, intriguing substituent effects of TAPS were observed, in which electron-donating methoxy groups enhanced their reactivity. In addition, the mechanism was thoroughly investigated by undertaking theoretical studies, suggesting that the electronic properties of TAPS affect carbon dioxide insertion into halohydrin intermediates.

Academic Significance and Societal Importance of the Research Achievements

本研究は、計算化学的アプローチをベースとした反応開発を行うことにより、従来とは方向性の異なる有機分子触媒反応開発の方法論を導き出すという発想に基づいている。本研究の成果として、本アプローチは、付加環化反応や二酸化炭素固定化反応における有機触媒の設計に効力を発揮することを明らかにした。既存の有機分子触媒分野の枠を超えた、計算化学・合成化学・触媒化学からの複合的アプローチによる反応開発は、それぞれの分野の進歩に必須であり、学術的に大きな意義がある。また、時間的および金銭的コストを削減した効率的プロセスの開発に貢献できると考えられ、産業界に対しても大きな波及効果を及ぼすものと考えられる。

Report

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

    (16 results)

All 2019 2018 2017

All Journal Article (7 results) (of which Peer Reviewed: 7 results) Presentation (9 results) (of which Int'l Joint Research: 2 results)

  • [Journal Article] Catalytic Asymmetric 1,3-Dipolar Cycloaddition Reactions Based on Ylide Formation Reactions2019

    • Author(s)
      Hiroyuki Suga, Yasunori Toda
    • Journal Title

      Journal of Synthetic Organic Chemistry, Japan

      Volume: 77 Issue: 10 Pages: 1014-1022

    • DOI

      10.5059/yukigoseikyokaishi.77.1014

    • NAID

      130007724803

    • ISSN
      0037-9980, 1883-6526
    • Year and Date
      2019-10-01
    • 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] Enantioselective synthesis of 8-azabicyclo[3.2.1]octanes via asymmetric 1,3-dipolar cycloadditions of cyclic azomethine ylides using a dual catalytic system2019

    • Author(s)
      Hiroyuki Suga, Masahiro Yoshiwara, Takaaki Yamaguchi, Takashi Bando, Mizuki Taguchi, Ayano Inaba, Yuichi Goto, Ayaka Kikuchi, Kennosuke Itoh, Yasunori Toda
    • Journal Title

      Chemical Communications

      Volume: 55 Issue: 11 Pages: 1552-1555

    • DOI

      10.1039/c8cc09224a

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Journal Article] Enantioselective Cycloadditions Between Aliphatic Nitrile Oxides and 2-Hydroxystyrenes Catalyzed by Chiral Amine-urea2018

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

      Heterocycles

      Volume: 97 Issue: 1 Pages: 147-147

    • DOI

      10.3987/com-17-s(t)7

    • Related Report
      2018 Research-status Report 2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] Triethylamine Enables Catalytic Generation of Oxidopyrylium Ylides for [5+2] Cycloadditions with Alkenes: An Efficient Entry to 8-Oxabicyclo[3.2.1]octane Frameworks2018

    • Author(s)
      Yasunori Toda, Masahiro Shimizu, Taichi Iwai, Hiroyuki Suga
    • Journal Title

      Adv. Synth. Catal.

      Volume: 印刷中 Issue: 12 Pages: 2377-2381

    • DOI

      10.1002/adsc.201800290

    • NAID

      120007099649

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Journal Article] Three-Component Reactions of Diazoesters, Aldehydes, and Imines Using a Dual Catalytic System Consisting of a Rhodium(II) Complex and a Lewis Acid2018

    • Author(s)
      Yasunori Toda, Wakatake Kaku, Makoto Tsuruoka, Sho Shinogaki, Tomoka Abe, Hideaki Kamiya, Ayaka Kikuchi, Kennosuke Itoh, Hiroyuki Suga
    • Journal Title

      Org. Lett.

      Volume: 20 Issue: 9 Pages: 2659-2662

    • DOI

      10.1021/acs.orglett.8b00865

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Journal Article] Amine-Urea-Mediated Asymmetric Cycloadditions between Nitrile Oxides and o-Hydroxystyrenes by Dual Activation2017

    • Author(s)
      Hiroyuki Suga, Yohei Hashimoto, Yasunori Toda, Kazuaki Fukushima, Hiroyoshi Esaki, Ayaka Kikuchi
    • Journal Title

      Angew. Chem. Int. Ed.

      Volume: 56 Issue: 39 Pages: 11936-11939

    • DOI

      10.1002/anie.201705662

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Presentation] Lewis acid-catalyzed alcohol addition reactions to cyclic carbonyl ylides generated from diazoacyloxazolidinones2019

    • Author(s)
      Takayuki Yoshida, Kaoru Arisue, Hiroyoshi Esaki, Kazuaki Fukushima, Yasunori Toda, Hiroyuki Suga
    • Organizer
      27th International Society of Heterocyclic Chemistry Congress
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research
  • [Presentation] ルイス酸触媒による非環状カルボニルイリドとアルデヒドの不斉付加環化反応2019

    • Author(s)
      佐藤建輔, 長崎一真, 中嶋紘崇, 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] キラルルイス酸触媒によるカルボニルイリドとアルデヒドの不斉付加環化反応2019

    • Author(s)
      長崎一真, 佐藤建輔, 中嶋紘崇, 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] ロジウム錯体とルイス酸の二成分触媒によるカルボニルイリドとイミンの1,3-双極性付加環化反応2018

    • Author(s)
      鶴岡信, 伊藤謙之介, 戸田泰徳, 菅 博幸
    • Organizer
      第48回複素環化学討論会
    • Related Report
      2018 Research-status Report
  • [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] 芳香族ニトリルオキシドと2-ヒドロキシスチレン類の不斉付加環化反応の反応機構解析と脂肪族ニトリルオキシドへの応用2018

    • Author(s)
      小山將人, 江嵜啓祥, 福島和明, 戸田泰徳, 菅 博幸
    • Organizer
      第48回複素環化学討論会
    • Related Report
      2018 Research-status Report
  • [Presentation] ニトリルオキシドと2-ヒドロキシスチレン類の不斉付加環化反応を基盤とする1,3-双極子の探索2018

    • Author(s)
      小山將人, 江嵜啓祥, 福島和明, 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] キラルアミン-ウレア触媒を用いる脂肪族ニトリルオキシドと2-ヒドロキシスチレン類の不斉付加環化反応2018

    • Author(s)
      小山 將人,江嵜 啓祥,福島 和明,戸田 泰徳,菅 博幸
    • Organizer
      日本化学会第98春季年会
    • Related Report
      2017 Research-status Report
  • [Presentation] Chiral Amine-urea Mediated Asymmetric Cycloadditions of Nitrile Oxides with o-Hydroxystyrenes and their Computational Studies for Asymmetric Induction2017

    • Author(s)
      Hiroyuki Suga, Yohei Hashimoto, Yasunori Toda, Kazuaki Fukushima, Hiroyoshi Esaki
    • Organizer
      26th International Society of Heterocyclic Chemistry Congress
    • Related Report
      2017 Research-status Report
    • Int'l Joint Research

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Published: 2017-07-21   Modified: 2021-02-19  

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