Challenge to Enantioselective C-F Bond Activation

2014 Fiscal Year Final Research Report

• Project/Area Number: 24655073
• Research Category: Grant-in-Aid for Challenging Exploratory Research
• Allocation Type: Multi-year Fund
• Research Field: Synthetic chemistry
• Research Institution: Gunma University
• Principal Investigator: AMII Hideki 群馬大学, 大学院理工学府, 教授 (00284084)
• Project Period (FY): 2012-04-01 – 2015-03-31
• Keywords: 有機合成化学 / フッ素 / 不活性結合 / 不斉反応 / 脱フッ素化 / クロスカップリング / 選択的変換

Outline of Final Research Achievements

Organofluorine compounds are widely used as materials such as polymer, liquid crystals, pharmaceutical and agrochemical compounds, and so on. Meanwhile, a new technology for highly selective synthesis of enantiomerically pure organofluorine compounds has been required. Toward stereoselective C-F bond activation, we examined Lewis acid-mediated defluorinative alkylation using gem-difluoromethylene compounds. Organoaluminum compounds were found to promote C-F bond activation of β-fluoro ethanol derivativess. When β, β-difluoro ethanols were treated with a stoichiometric amount of trimethylaluminum, defluorination and the subsequent methylation proceeded smoothly to give the ketones in moderate yields. For the preparation of several gem-difluoromethylene substrates, we developed the cross-coupling routes to 2-aryl-2,2-difluoroacetates. Furthermore, a new strategy for the synthesis of monofluoro compounds involving Mg-promoted defluorination of 2-aryldifluoroacetates have been invented.

Free Research Field

有機合成化学