Pd-catalyzed arylation of silyl enol ethers of substituted α-fluoroketones

Abstract

α-Fluoro-α-aryl-ketones were synthesized by the Pd-catalyzed cross-coupling of aryl bromides with either α-fluoroketones or their corresponding silyl enol ethers. The direct arylation with an α-fluoroketone requires a strong base, such as potassium tert-butoxide, and under these conditions the presence of a base-sensitive functional group is not compatible. However, good functional tolerance was achieved when the anionic coupling moieties were generated from the silyl enol ethers obtained by reacting α-fluoroketones with tetrabutylammonium (tripheny1silyl) difluorosilicate (TBAT) as the fluoride source under nearly neutral conditions. The aryl halides with a carbmethoxy, nitro, cyano or carbonyl group were used. The reaction with nonfluorinated silyl enol ether 1h gave a cross-coupling product in low yield. © 2009 The Royal Society of Chemistry.