Direct Access to Aminocyclopentenones through Rh‐Catalyzed Cascade Wolff Rearrangement and Decarbonylative Amination

The cascade reaction of cyclic 2‐diazo‐1,3‐diketones and diarylamines is efficiently developed, enabling straightforward access to a series of 2‐aminocyclopentenones in good to excellent yields (71–90%). The procedure is proposed to go through a sequence of Wolff rearrangement via initial ketene formation, nucleophilic addition/keto‐enol tautomerization, and Rh 2 (OAc) 4 ‐catalyzed decarbonylative amination followed by an oxidation process. A broad range of substrates are compatible with this mild reaction system, thereby providing a facile and practical approach for constructing important skeleton of aminocyclopentenone.