Palladium-catalyzed regioselective Heck arylation of electron-rich olefins in a molecular solvent-ionic liquid cocktail

摘要

We have recently established that highly regioselective Heck arylation of electron-rich olefins can be accomplished with aryl halides without using any halide scavengers in imidazolium ionic liquid solvents. The results presented in this paper show that the benchmark electron-rich olefins vinyl ethers can be readily arylated by aryl bromides in a molecular solvent-ionic liquid cocktail with no compromise on regioselectivity. By introducing a small amount of 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF4]) to DMSO, the arylation reactions of the vinyl ethers 1a-d by the bromides 2a-j took place to afford essentially only the alpha arylated products. The enamide 1e underwent similar regioselective arylation in the solvent cocktail. In the absence of the ionic liquid, lower regioselectivities were observed. In comparison with the chemistry we have reported so far, the current method reduces considerably the reliance on the volume of ionic liquids used, providing a simpler and more practical synthetic pathway for preparing arylated vinyl ethers and aryl methyl ketones. (c) 2005 Elsevier Ltd. All rights reserved.