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Updated: Jul 28, 2025

Characterizing Lewis Pairs Using Titration Coupled with In Situ Infrared Spectroscopy
Published on: February 20, 2020
An Asynchronous Concerted Mechanism and Its Origin in Lewis Acid-Mediated Carbonyl-Olefin [2+2] Cycloaddition
Yan-Yu Li1, Shuo-Qing Zhang1, Xin Hong1,2,3,4
1Center of Chemistry for Frontier Technologies, Department of Chemistry, State Key Laboratory of Clean Energy Utilization, Zhejiang University, Hangzhou, 310027, P. R. China.
Abstract:
The concerted mechanism of thermal BBr3 -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.
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