The [4+2] Diels-Alder cycloaddition reaction represents a widely used method in both classical and modern organic chemistry for constructing cyclic systems. An intriguing approach includes the use of azadienes for the aza-Diels-Alder reaction as a key step of the transformation. For instance, β-styrylsaccharin 44 is involved in a cascade asymmetric organocatalytic reaction with 2,5-dienone 45, featuring a reactive malononitrile fragment. Using of salicylic acid in toluene and quinine derivative 46 as a catalyst, the corresponding polycyclic product 47 could be obtained in enantiomerically and diastereomerically pure form (Scheme 4). Scheme 4. Cascade reaction of aza-Diels-Alder with the formation of sultam 47