The wide scope of nucleophilic partners in this multicomponent reaction prompted an exploration of its applicability to the late-stage functionalization of intricate pharmaceutical compounds. Gratifyingly, the methodology exhibited remarkable versatility, encompassing a wide spectrum of intricate amines, spanning both drug molecules and their derivatives (Scheme 2). Cyclic amines from Loratadine (39c), Norquetiapine (40c), Cytisine (41c), Donepezil (42c), Semap (43c), Ibrutinib (44c), Paroxetine (45c), Flunarizine (46c), Fenoldopam (47c), and Sildenafil (48c) served as amenable substrates, providing medium to good yields of the complex difluoromethylated tertiary amine products. Similarly, the acyclic secondary amine of Fluoxetine (49c) underwent conversion to the corresponding product in 80% yield. Furthermore, the free amino ester could be employed as nucleophile to furnish the desired product (50c) in 50% yield. Next, various 1,3-dienes incorporating common functional groups were subjected to our protocol. The manifold adeptly delivered the desired products while bearing functional groups such as alkene (53c), ester (54c), ether (55c), free primary alcohol (56c), OTBS (57c), and amino acid derivative (58c) on the conjugated diene, showcasing the remarkable functional group tolerance of this method. However, for the phenylsubstituted 1,3-diene substrate, the reaction exhibited diminished reactivity, affording only 30% of the desired product (59c), potentially attributable to steric hindrance effects. Then the butadiene with minimum steric effect was tested and exhibited very good reactivity, yielding the desired product (60c) in 95% yield. Notably, in all cases, we only observed the 1,4adiition products with E-geometry double bond. Moreover, while using all the cheap and readily available industrial stocks including benzylamine, butadiene and Freon-22, the in situ formed secondary amine could serve as a new nucleophile to afford the complex tertiary amine as the final product (61c) with 62% yield in a gram scale set up which further showcased its utility (eq 1).