Switching the N‐Alkylation of Arylamines with Benzyl Alcohols to Imine Formation Enables the One‐Pot Synthesis of Enantioenriched α‐N‐Alkylaminophosphonates

The selective N ‐alkylation of anilines with benzylic alcohols can be switched in favor of the dehydrogenative condensation process using the nitrile‐ligated Knölker's complex by conducting the reaction either in a closed system under inert conditions, or in an open system in air. The selective formation of imines, containing reactive C=N bonds, provides an opportunity towards further functionalization. Indeed, a one‐pot three‐component condensation of alcohols, amines and phosphites, promoted by an iron‐based Knölker‐type complex in combination with a chiral BINOL‐based phosphoric acid, provides access to enantioenriched α‐ N ‐alkylaminophosphonates.