Migratory Hydroamination of Alkenes via Iron-Hydride Catalysis

Abstract The renaissance of catalytic metal hydride hydrogen atom transfer (MHAT) offers advanced tools for hydroamination of alkenes. Despite these merits, state-of-the-art MHAT hydroamination protocols are largely limited to intermolecular coupling or intramolecular cyclization, thereby necessitating new catalytic platforms to explore MHAT reactivity and access unexplored hydroamination reaction pathways. Herein, we report an iron hydride-catalyzed migratory hydroamination of allylamines, enabled by a sequential MHAT process with finely tuned 1,2-amino migration. This strategy converts readily accessible allylamines into structurally diverse alkylamines and β-amino acids through a three-step radical cascade. This protocol features a broad tolerance toward a range of functional groups, encompassing complex drug and natural product derivatives. Beyond providing an efficient approach to medicinally relevant amine scaffolds, this work establishes a new paradigm for MHAT-enabled molecular editing through radical functional group migration, thereby expanding the synthetic repertoire of alkene hydroamination.