The construction of multisubstituted β-pyrrolinones from simple starting materials remains a great challenge. Recently, a novel Cu(I)-catalyzed [2 + 2 + 1] cycloaddition reaction was developed for rapid access to fully substituted β-pyrrolinones, which are difficult to synthesize through traditional methods as this approach may involve unusual C-nucleophilic addition of enamines and umpolung of imines. Elucidating the reaction mechanism may inspire the development of new methodologies via the unusual C-nucleophilic addition of enamines and imines. However, the reaction mechanism is still unclear because none of the intermediates was observed during the reaction process. In this work, we employed theoretical and computational chemistry to investigate the possible pathway. Finally, the calculated results indicate that ketene formed by the Wolff rearrangement of α-diazo-β-ketoester reacts with enamine formed by the addition of alkynes and amine, affording the five-membered azaheterocycle, and this process involves the formation of a six-membered ring intermediate and sequential isomerization, and the further dehydrogenation needs to be assisted with solvent MeNO2.