A New Methodology for Preparing Benzylated Aminopyridines Yields Previously Inaccessible Organocatalysts

p‐Dialkylaminopyridines represent a key class of nucleophilic organocatalysts, widely used in alcohol‐modifying reactions, among other applications. However, access to certain variants of these catalysts, particularly those with sterically congested secondary sphere, remains challenging or even unfeasible using previously established synthetic routes. Lewis acid‐promoted benzylation or cyclative dibenzylation of simple aminopyridines with corresponding alcohols effectively overcomes these shortcomings. This innovative approach enables the synthesis of previously inaccessible (2,5‐diarylpyrrolidino)pyridines and novel (N‐benzyl‐N‐methylamino)pyridines bearing extended ortho‐alkoxy tails on the aryl substituents. The new catalysts, characterized by their bulky secondary sphere, exhibit outstanding activity and high site‐selectivity in the phosphorylation of a model diol amphiphile.