Counterion effects in iminium-activated electrophilic aromatic substitutions of pyrroles

Abstract

Electrophilic substitution of pyrroles by α,β-unsaturated iminium ions is slow in acetonitrile when only weakly basic counterions are present. When the reactions are carried out in the presence of KCF₃CO₂, fast deprotonation of the intermediate σ-adducts occurs, and the rate constant for the rate-determining CC bond-forming step can be predicted from the electrophilicity parameter E of the iminium ion and the N and s parameters of the pyrroles.