Diarylprolinol silyl ethers immobilized onto polystyrene have been employed as catalysts in the enantioselective domino Michael-Knoevenagel reaction of dimethyl 3-oxoglutarate and 3-substituted acrolein derivatives, including aliphatic ones. The best catalyst allows the preparation of highly functionalized cyclohexane derivatives in a straightforward and efficient manner, both under batch and continuous flow conditions.