Nucleophilic Catalysis by 4‐(Dialkylamino)pyridines Revisited—The Search for Optimal Reactivity and Selectivity

A complex interplay between catalyst structure, acylating agent, auxiliary base, and solvent governs the reactivity and selectivity in 4-(dialkylamino)pyridine-catalyzed esterification reactions (see scheme). This highlight attempts a rationalization of the complicated mechanism and puts forward some explanations for seemingly contradictory experimental observations.