Development of Perfluoroalkylation Reactions based on Organozinc Reagents

2015 Fiscal Year Final Research Report

• Project/Area Number: 26860010
• Research Category: Grant-in-Aid for Young Scientists (B)
• Allocation Type: Multi-year Fund
• Research Field: Chemical pharmacy
• Research Institution: The University of Tokyo
• Principal Investigator: HIRANO KEIICHI 東京大学, 薬学研究科(研究院), 助教 (40633392)
• Project Period (FY): 2014-04-01 – 2016-03-31
• Keywords: パーフルオロアルキル化 / パーフルオロアリール化 / フッ素 / 亜鉛 / ハロゲンー金属交換

Outline of Final Research Achievements

We developed facile and efficient methods for preparation of RF-zinc species via halogen-zinc exchange between RF-X and dialkylzincs activated by Lewis bases. A stable RF-zincate, RFZn(Cl)MeLi, is generated by using LiCl as an activator and this zinc reagent efficiently perfluoroalkylates various carbonyl compounds at rt. Use of DMPU as an activator forms even more thermally stable RF-zinc, RFZnR(dmpu), and this zinc reagent participates in copper-catalyzed cross-coupling with aryl halides at 120°C. The excellent thermal stability of RF-zinc reagents compares favorably with the Li- and Mg-counterparts, which require cryogenic reaction conditions, and will certainly find further applications. Moreover, we have discovered the allylic polyfluoroarylation reaction of allylic bromides using ArF-Zn activated by phosphine oxides.

Free Research Field

有機化学