A para‐toluenesulfonic acid (pTSA) catalyzed domino aza‐Piancatelli rearrangement/Michael reaction was developed for the construction of 1,4‐benzodiazepin‐5‐ones in one pot. The method proceeds well in the presence of various furfurylcarbinols and o‐aminobenzamides to give products that contain medicinally relevant chemical entities.

A new and efficient approach to a series of novel multifunctionalized spirocyclopentenone scaffolds through Piancatelli rearrangement was developed under metal-free conditions. The method has been successfully applied to O-, N-...