Mechanistic Investigation of DBU-Based Ionic Liquids for Aza-Michael Reaction: Mass Spectrometry and DFT Studies of Catalyst Role

1,8-Diazabicyclo[5.4.0]undec-7-ene (DBU)-based ionic liquids (ILs) has exhibited a high catalytic activity in the aza-Michael reactions compared to conventional catalysts and with imidazole-based ILs. In the present work DBU-based ILs showed high catalytic potential for aza-Michael addition of aromatic amines to 2-cyclohexen-1-one under solvent-free condition. Electrospray ionization-mass spectrometry (ESI-MS) and density functional theory studies have been carried out to provide an effective activation mode of DBU-based ILs in aza-Michael addition. Our results show that both the presence of the acid hydrogen in the IL and the ability of the anion to carry out a hydrogen bond with the − NH2 group of the arylamine are fundamental for the reaction catalysis. The catalytic model proposed can be used for the rational development of new ILs with excellent catalytic properties.
Source: Journal of the Brazilian Chemical Society - Category: Chemistry Source Type: research