The study began with the evaluation of aldehydes using formaldehyde aqueous solution, the most elementary aldehyde. As an appealing CH2 synthon, formaldehyde successfully bridged the amine and boron species (75), leading to the homologation/amination of alkyl boronic acids and demonstrating the water compatibility of this process. The coupling process with a diverse set of primary aldehydes (76-80) was also successful, showcasing tolerance with numerous functional groups. Secondary aldehydes, particularly with saturated cyclic and heterocyclic rings, exhibited good reactivity, generating several sterically hindered tertiary amines (81-87). The scope of this APBM transformation was further expanded to include substituted benzaldehydes (89-92) and heteroaryl aldehydes (88, 93), both of which were compatible under these conditions, yielding (hetero)benzylic tertiary amines with moderate to good yields. This method was effectively applied to swift derivatization of chlorambucil ( ), where an analogue was prepared with 68% yield.