Elucidating the Key Factors in Hydroamination and Defluoroamination Competitions: A DFT Analysis of Reaction between α‐(Trifluoromethyl)styrene and 2‐Pyridones

Abstract

Abstractβ‐fluorocarbanions have garnered considerable attention for their dual reactivity in nucleophilic processes and β‐fluorine elimination. In this study, a thorough computational analysis was conducted to explore the reactions of α‐(trifluoromethyl)styrenes with 2‐pyridones to delineate the factors determining protonation or defluorination pathways for the in situ generated β‐fluorocarbanions under varied basic conditions. Our findings illuminate the critical role of organobase basicity in steering the direction of the competitive protonation and β‐fluorine elimination reactions. We propose the use of pKaH values of organobases as a quantitative indicator for discerning the predominant reaction pathways. This provides an efficient approach to predict and control the reaction outcome, facilitating the deliberate design of reactions to leverage the unique reactivity of β‐fluorocarbanions in the realm of fluorine chemistry.