Development of photo-induced radical generation based on triazinylammonium salt

• Project/Area Number: 16K08160
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Research Field: Chemical pharmacy
• Research Institution: Kanazawa University
• Principal Investigator: Yamada Kohei 金沢大学, 薬学系, 助教 (40583232)
• Project Period (FY): 2016-04-01 – 2019-03-31
• Project Status: Completed (Fiscal Year 2018)
• Budget Amount: ¥4,810,000 (Direct Cost: ¥3,700,000、Indirect Cost: ¥1,110,000); Fiscal Year 2018: ¥1,040,000 (Direct Cost: ¥800,000、Indirect Cost: ¥240,000); Fiscal Year 2017: ¥1,820,000 (Direct Cost: ¥1,400,000、Indirect Cost: ¥420,000); Fiscal Year 2016: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000)
• Keywords: トリアジニルアンモニウム塩 / 光レドックス触媒 / トリアジン / 光反応 / ラジカル / 有機化学

Outline of Final Research Achievements

I have developed a method for photo-induced alkyl radical generation based on triazinylammonium salt. Direct radical generation by UV irradiation to triazinylammonium salt has proved to be difficult. On the other hand, the reaction of triazinylammonium salt in the presence of a metal photoredox catalyst and a reducing agent under visible light irradiation allowed to generate the alkyl radical, which subsequently reacted with the coexisting Michael acceptor to give the desired adduct in a 73% yield

Academic Significance and Societal Importance of the Research Achievements

有機化学において、あらゆる官能基を自在に操り合成することは究極的な目標の一つである。水酸基やカルボキシ基、アミノ基は自然界に多く存在する官能基である。水酸基やカルボキシ基は数多くの官能基変換法が開発されている一方で、アミノ基を他の官能基に置換する実用的な方法は極めて少ない。そのため、種々の官能基存在下、自在にアミノ基を他の官能基に変換できるようになれば、多様な有機合成の局面において、極めて有効な手法となり得る。

Research Products

• [Journal Article] Development of triazine-based esterifying reagents containing pyridines as a nucleophilic catalyst (2018)
  • Author(s): Kohei Yamada, Jie Liu, Munetaka Kunishima
  • Journal Title: Org. Biomol. Chem. Volume: 16 Pages: 6569-6575
  • Peer Reviewed
• [Journal Article] Imido-substituted triazines as dehydrative condensing reagents for the chemoselective formation of amides in the presence of free hydroxy?groups (2018)
  • Author(s): Kitamura Masanori、Sasaki Suguru、Nishikawa Riho、Yamada Kohei、Kunishima Munetaka
  • Journal Title: RSC Advances Volume: 8 Issue: 40 Pages: 22482-22489
  • DOI: 10.1039/c8ra03057j
  • Peer Reviewed / Open Access
• [Journal Article] An Isolable and Bench-Stable Epoxidizing Reagent Based on Triazine: Triazox (2018)
  • Author(s): Yamada Kohei、Igarashi Yuki、Betsuyaku Tatsuki、Kitamura Masanori、Hirata Koki、Hioki Kazuhito、Kunishima Munetaka
  • Journal Title: Organic Letters Volume: 20 Issue: 7 Pages: 2015-2019
  • DOI: 10.1021/acs.orglett.8b00560
  • Peer Reviewed
• [Journal Article] Development of Triazine-Based Benzylating Reagents Possessing <i>t</i>-Butyl Group on the Triazine Core: Thermally Controllable Reagents for the Initiation of Reaction (2018)
  • Author(s): Karuo Yukiko、Yamada Kohei、Kunishima Munetaka
  • Journal Title: Chemical and Pharmaceutical Bulletin Volume: 66 Issue: 3 Pages: 303-308
  • DOI: 10.1248/cpb.c17-00897
  • NAID: 130006407119
  • ISSN: 0009-2363, 1347-5223
  • Peer Reviewed