An Asynchronous Concerted Mechanism and Its Origin in Lewis Acid‐Mediated Carbonyl‐Olefin [2+2] Cycloaddition

Abstract

The concerted mechanism of thermal BBr 3 -mediated [2 + 2] carbonyl-olefin cycloaddition is intriguing considering the conflict against the Woodward-Hoffmann rule. In this work, we report a mechanistic study of the titled reaction using density functional theory calculations. The concerted [2 + 2] cycloaddition mechanism is operative even for the truncated model system of 2-methyl-2-butene and butanone.Intrinsic reaction coordinate analysis and potential surface mapping showed the asynchronous nature of the apparent concerted [2 + 2] cycloaddition, resulting from the proximity of carbocation-oxyanion in the transient zwitterionic structure. Solvent effects can change the reaction to a stepwise mechanism, highlighting the importance of zwitterion stability. Building upon this finding of the asynchronous concerted or stepwise [2 + 2] cycloaddition mechanism, two mechanistic classifications were elaborated based on substrates containing varied substituents and Lewis acids, with a focus on manipulating the stability of positive carbocation and negative oxyanion in the transient zwitterionic species.