Lewis Acid-Relayed Singlet Oxygen Reaction with Enamines: Selective Dimerization of Enamines to Pyrrolin-4-ones

Singlet oxygen (¹O₂)-mediated oxidation represents an attractive strategy for incorporation of oxygen atoms from air under mild and environmentally benign conditions. However, the ¹O₂ reaction with enamine suffers from fragmentation, leading to very unsuccessful transformation. Here, Lewis acid is introduced to intercept [2 + 2] or "ene" reaction intermediates of the ¹O₂ reaction and enables oxidative dimerization of enamines to produce pyrrolin-4-ones in good to excellent yields. Mechanistic studies reveal the formation of the imino ketone intermediate from the interaction of ¹O₂ and enamine, which is able to interact with Lewis acid, relaying the ¹O₂ reaction in enamine chemistry. For the first time, selective cross-dimerization of two different enamines is achieved. Due to the advantages of mild conditions, high chemoselectivity, and up to 99% yield, a promising strategy has been developed for synthesizing aza-heterocycles under ambient conditions, which can be further applied for the synthesis of imidazolone, quinoxaline, and highly functionalized imine.