Development of trifluoromethylation reaction by using a novel chiral hypervalent iodine catalyst

• Project/Area Number: 15K17860
• Research Category: Grant-in-Aid for Young Scientists (B)
• Allocation Type: Multi-year Fund
• Research Field: Synthetic chemistry
• Research Institution: Institute of Physical and Chemical Research
• Principal Investigator: Kawamura Shintaro 国立研究開発法人理化学研究所, 環境資源科学研究センター, 研究員 (60732956)
• Project Period (FY): 2015-04-01 – 2018-03-31
• Project Status: Completed (Fiscal Year 2017)
• Budget Amount: ¥4,290,000 (Direct Cost: ¥3,300,000、Indirect Cost: ¥990,000); Fiscal Year 2017: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000); Fiscal Year 2016: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000); Fiscal Year 2015: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
• Keywords: トリフルオロメチル化 / 過酸化トリフルオロアセチル / 超原子価ヨウ素

Outline of Final Research Achievements

Trifluoromethylated compounds as drugs and medicines have attracted much attention due to improved pharmaceutical activity. Based on my previous work, I designed a stereoselective trifluoromethylation of alkenes by using hypervalent iodine catalyst. A combination of oxidants and CF3 sources is important to achieve the reaction and was examined carefully. As the result, a fluoro diacyl peroxide was found to be available for the each steps in the catalytic cycle of the desired reaction.

Research Products

• [Journal Article] Synthesis of CF3-containing oxazolines via trifluoromethylation of allylamides with Togni reagent in the presence of alkali metal iodides (2017)
  • Author(s): Kawamura Shintaro、Sekine Daisuke、Sodeoka Mikiko
  • Journal Title: Journal of Fluorine Chemistry Volume: 203 Pages: 115-121
  • DOI: 10.1016/j.jfluchem.2017.07.012
  • Peer Reviewed / Open Access
• [Journal Article] N-Heterocycle-forming amino- and carbo-perfluoroalkylations of aminoalkenes by using perfluoro acid anhydrides: mechanistic studies and applications directed toward perfluoroalkylated compound libraries (2017)
  • Author(s): Shintaro Kawamura, Kento Dosei, Elena Valverde, Kiminori Ushida, Mikiko Sodeoka
  • Journal Title: J. Org. Chem. Volume: 82 Issue: 23 Pages: 12539-12553
  • DOI: 10.1021/acs.joc.7b02307
  • Peer Reviewed
• [Journal Article] Perfluoroalkylation of Unactivated Alkenes with Acid Anhydrides as the Perfluoroalkyl Source (2016)
  • Author(s): Shintaro Kawamura, Mikiko Sodeoka
  • Journal Title: Angew. Chem. Int. Ed. Volume: 55 Issue: 30 Pages: 8740-8743
  • DOI: 10.1002/anie.201604127
  • Peer Reviewed / Acknowledgement Compliant
• [Presentation] Development of a synthetic method for perfluoroalkylated N-heterocycles directed toward construction of compound libraries (2018)
  • Author(s): Shintaro Kawamura, Kento Dosei, Elena Valverde, Kiminori Ushida, Mikiko Sodeoka
  • Organizer: 日本化学会 第98春季年会
• [Presentation] Development of perfluoroalkylation of unactivated alkenes by using perfluoro acid anhydrides (2017)
  • Author(s): Shintaro Kawamura, Mikiko Sodeoka
  • Organizer: 第97日本化学会春季年会
  • Place of Presentation: 慶應大学 (横浜)
  • Year and Date: 2017-03-16
• [Presentation] Practical Electrophilic Perfluoroalkylation of Alkenes (2016)
  • Author(s): 河村伸太郎、袖岡幹子
  • Organizer: French-Japanese Symposium on Medicinal and Fine Chemistry
  • Place of Presentation: 京王プラザホテル（東京・多摩）
  • Year and Date: 2016-05-15
  • Int'l Joint Research
• [Presentation] 実用的なペルフルオロアルキル化反応の開発 (2016)
  • Author(s): 河村伸太郎
  • Organizer: 平成28年度若手研究者のためのセミナー
  • Place of Presentation: 東京大学 (東京)
  • Invited
• [Patent(Industrial Property Rights)] パーフルオロアルキル化化合物の製造方法 (2016)
  • Inventor(s): 袖岡幹子、河村伸太郎
  • Industrial Property Rights Holder: 理化学研究所
  • Industrial Property Rights Type: 特許
  • Filing Date: 2016-12-12
  • Overseas
• [Patent(Industrial Property Rights)] パーフルオロアルキル化化合物の製造方法 (2015)
  • Inventor(s): 袖岡幹子、河村伸太郎
  • Industrial Property Rights Holder: 理化学研究所
  • Industrial Property Rights Type: 特許
  • Filing Date: 2015-12-05