Branched‐Selective Functionalization of 2‐Alkyl Aziridines Through Ni‐Catalyzed Dynamic Kinetic Activation

Abstract 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.