Unified Synthesis of Unconventional α‐Polyhalogenated Amines Through Hydroaminoalkylation

We report a unified method for the synthesis of α‐polyhalomethyl amines from alkenes and alkynes, enabled by readily available hemiaminal reagents. This operationally simple transformation allows for the introduction of not only well‐established CF 3 and CF 2 H groups, but also the synthetically (and medicinally) underexplored CF 2 Cl and CFClH motifs—thereby broadening access to previously inaccessible chemical space of halogenated amine scaffolds. The method displays broad substrate scope and functional‐group tolerance while operating under mild conditions. Late‐stage functionalization of drug‐like derivatives of Oxaprozin, Erlotinib, and Ibuprofen (among others) is reported.