Dedicated to Professor Julio Alvarez-Builla on occasion of his 65 th birthday Abstract (S)-Binam-L-prolinamide (20 mol%) catalyze the enantioselective Michael addition of several α-alkoxyketones to different β-nitrostyrene derivatives. In the study of the optimization of the reaction conditions it was found surprisingly that hexane is the solvent of choice to carry out such transformation. Under these reaction conditions, the corresponding highly functionalized products were obtained in good yields (up to 90%), mainly as syn-diastereomers with moderate diastereoand enantioselectivities.