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Overriding the inherent substrate-controlled regioselectivity in aziridine activation holds significant potential. It could enable previously inaccessible disconnections from these readily available, strained heterocycles, facilitating the diverse synthesis of nitrogen-containing products. In this study, we present a Ni-catalyzed dynamic kinetic activation of 2-alkyl (and 2,2-dialkyl) aziridines, leading to unconventional branched-selective alkyl Heck-type coupling with styrenes and reductive defluorinative coupling with trifluoromethyl alkenes. In addition to enabling the functionalization of the N-adjacent sites of aziridines, this catalyst-controlled activation strategy triggers an unprecedented reaction framework for aziridines, namely, the remote desaturation via ring-opening. Notably, detailed mechanistic studies demonstrate the operation of a rare “self-terminated” chain-walking process, offering a flexible method for remote desaturation that generates alkenyl amines with varying chain lengths. Overall, this study provides a modular approach to access a wide range of alkenyl amine derivatives.