Design and development of the reactions using organocatalyst by computational screening
| Project/Area Number |
17KT0096
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Multi-year Fund |
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| Section | 特設分野 |
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| Research Field |
Transition State Control
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| Research Institution | Shinshu University |
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Principal Investigator |
Suga Hiroyuki 信州大学, 学術研究院工学系, 教授 (60211299)
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| Co-Investigator(Kenkyū-buntansha) |
戸田 泰徳 信州大学, 学術研究院工学系, 助教 (60758978)
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| Project Period (FY) |
2017-07-18 – 2020-03-31
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| Project Status |
Completed (Fiscal Year 2019)
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| 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)
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| 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 |
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| 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.
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| 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。
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Report
(4 results)
Research Products
(16 results)
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[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
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Journal Title
Chemical Communications
Volume: 55
Issue: 11
Pages: 1552-1555
DOI
Related Report
Peer Reviewed
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[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
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Journal Title
Org. Lett.
Volume: 20
Issue: 9
Pages: 2659-2662
DOI
Related Report
Peer Reviewed
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