Decarboxylative Route to Organofluorine Compounds

2016 Fiscal Year Final Research Report

• Project/Area Number: 25288044
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Partial Multi-year Fund
• Section: 一般
• Research Field: Synthetic chemistry
• Research Institution: Gunma University
• Principal Investigator: Amii Hideki 群馬大学, 理工学府, 教授 (00284084)
• Co-Investigator(Kenkyū-buntansha): 園山 正史 群馬大学, 大学院理工学府, 教授 (40242242)
• Project Period (FY): 2013-04-01 – 2017-03-31
• Keywords: 有機合成化学 / フッ素 / 脱炭酸 / 炭素―炭素結合形成 / ヘテロ元素化合物 / ラジカル反応

Outline of Final Research Achievements

Fluorine-containing organic molecules play a pivotal role in the remarkable progress of medicinal, agricultural, and material sciences. Difluoromethylene compounds have been considerable synthetic targets because of their wide utility. Among them, difluoromethylated aromatic compounds (Ar-CF2-R) have received a great deal of attention in the design of bioactive molecules. Previously, we reported the reaction sequence involving cross-coupling and decarboxylation to afford difluoromethyl aromatics (Ar-CF2H). Herein we developed versatile decarboxylative transformations for the synthesis of aromatic compounds bearing functionalized difluoromethyl groups. Upon heating in DMSO or NMP at 170 °C with CuI, potassium 2-aryl-2,2-difluoroacetates underwent decarboxylation to generate aryldifluoromethyl anions (ArCF2-), which reacted with electrophiles to afford a variety of gem-difluoromethylene compounds in moderate to good yields.

Free Research Field

有機合成化学