Aza-Morita-Baylis-Hillman reactions of N-(benzylidene)polyfluoroanilines with methyl acrylate and acrylonitrile

Aza-Morita-Baylis-Hillman reactions of N-(benzylidene)polyfluoroanilines 1 with methyl acrylate or acrylonitrile were studied. It was found that Lewis base, solvent and reaction temperature can significantly affect the reaction. Using 3-hydroxyquinuclidine (3-HQD) as a Lewis base in the reactions of 1 with methyl acrylate in DMF, the normal aza-Morita-Baylis-Hillman adducts 3 were formed in moderate to excellent yields. For the reactions of 1 with acrylonitrile, 1,4-diazabicyclo[2.2.2]octane (DABCO) is the best Lewis base giving the corresponding aza-Morita-Baylis-Hillman adducts 4 as the sole product in good to moderate yield. However, upon treatment of 1 with acrolein 2c, the corresponding reaction did not occur even in the presence of a variety of catalysts.