Tris(aryl)cyclopropenium Ion as Organic Lewis Acid Catalyst in Carbonyl Activation Reactions

Although, in recent years, cyclopropenium salts have been explored as phase-transfer catalysts, electro-photocatalysts, H-bond donor catalysts, etc., and until now, they have not been utilized directly as Lewis acid catalysts in organic transformations. In this article, we demonstrate a "Proof of Concept" that the tris(aryl)cyclopropenium (TAC) carbocation could be utilized as an organic Lewis acid catalyst in some of the reactions involving carbonyl activation such as 1,2-addition reactions of aldehydes, 1,4-conjugate addition reactions of enones, and 1,6-vinylogous conjugate addition of dienones (p-quinone methides). The mode of activation of carbonyl group by cyclopropenium ion has been studied using NMR titrations and UV kinetics and further supported by computational calculations.