Generation of Aryl Radicals from Arylboronic acids and Benzoic Acids via Photoinduced Electron Transfer
| Project/Area Number |
17K05779
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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 | 一般 |
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| Research Field |
Organic chemistry
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| Research Institution | University of Fukui |
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Principal Investigator |
Yoshimi Yasuharu 福井大学, 学術研究院工学系部門, 准教授 (30345673)
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| Project Period (FY) |
2017-04-01 – 2020-03-31
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| Project Status |
Completed (Fiscal Year 2019)
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| Budget Amount *help |
¥4,810,000 (Direct Cost: ¥3,700,000、Indirect Cost: ¥1,110,000)
Fiscal Year 2019: ¥1,170,000 (Direct Cost: ¥900,000、Indirect Cost: ¥270,000)
Fiscal Year 2018: ¥910,000 (Direct Cost: ¥700,000、Indirect Cost: ¥210,000)
Fiscal Year 2017: ¥2,730,000 (Direct Cost: ¥2,100,000、Indirect Cost: ¥630,000)
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| Keywords | アリールラジカル / 安息香酸 / アリールボロン酸 / 光脱炭酸反応 / 光脱ボロン化反応 / 光レッドクス有機触媒 / 光誘起電子移動 / 光反応 / 光脱ボロン酸反応 / 有機光反応 / 芳香族ボロン酸 / 有機化学 |
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| Outline of Final Research Achievements |
Aryl radicals are useful reactive intermediates in reactions that introduce aryl groups. Typically, the generation of aryl radicals requires the use of stoichiometric amounts of toxic metals (Sn, Cu, Ag) and/or sensitive substrates such as aryl halides and aryl diazonium salts, as well as harsh reaction conditions such as high temperature. In particular, diazonium salts are often explosive and highly toxic, and diazonium salts bearing sensitive substituents cannot be used as substrates for generating aryl radicals.
In this study, we achieved mild generation of aryl radicals from arylboronic acids or benzoic acids using organic photoredox catalysts. The resulting aryl radicals react with electron-deficient alkenes and acetonitrile to furnish adducts and the reduction product, respectively. This is a first example of generation of aryl radicals using two-molecule organic photoredox system under mild conditions.
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| Academic Significance and Societal Importance of the Research Achievements |
安価で安定である光レドックス有機触媒を用いて、アリールボロン酸や安息香酸からアリールラジカルの生成およびその反応を見出した。温和な条件でアリールラジカルを生成できるため、今まで使用できなかった基質をこれらの反応に利用できる。これだけでなく、現在のラジカル化学に対する新しい手法を提案できた。これは、今までのラジカル反応では主にアルキルラジカルを活性種として用いてきたが、我々の見出した方法を用いてアリールラジカルが容易に発生させることができるため、新規なラジカル反応の開発が飛躍的に高まる可能性がある。
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Report
(4 results)
Research Products
(31 results)
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[Journal Article] Synthesis of 23-, 25-, 27-, and 29-Membered (Z)-Selective Unsaturated and Saturated Macrocyclic Lactones from 16- and 17-Membered Macrocyclic Lactones and Bromoalcohols by Wittig Reaction, Yamaguchi Macrolactonization, and Photoinduced Decarboxylative Radical Macrolactonization2019
Author(s)
T. Iwasaki, Y. Tajimi, K. Kameda, C. Kingwell, W. Wcislo, K. Osaka, M. Yamawaki, T. Morita, Y. Yoshimi
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Journal Title
The Journal of Organic Chemistry
Volume: 84
Issue: 12
Pages: 8019-8026
DOI
Related Report
Peer Reviewed / Int'l Joint Research
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