Remapping the Synthetic Landscape of α‐Tertiary Alkylamines via Dual‐Functional Catechol

ABSTRACT α‐Tertiary alkylamines are privileged motifs with a strong propensity to be bioactive, rendering their efficient synthesis fundamentally important across diverse areas of chemistry. Despite recent advances in aliphatic amine preparation, the direct construction of hindered α ‐tertiary amines remains a long‐standing challenge. Here, we report a three‐component assembly that exploits the dual role of catechol to enable the modular synthesis of these motifs from readily available, bench‐stable reactants. This method exhibits exceptional functional‐group tolerance and provides access to a variety of synthetically demanding molecular architectures, including consecutive quaternary centers as well as vicinal aminoether and diamine fragments. This approach, therefore, represents a valuable supplement to the chemist's toolbox for α ‐tertiary alkylamines, offering streamlined routes to complex targets and significant possibilities in drug discovery.