Iron‐Catalyzed Anti‐Markovnikov Hydroxyazidation of Unactivated Alkenes

ABSTRACT Anti‐Markovnikov oxidation of alkenes to access primary alcohols remains a significant synthetic challenge due to inherent regioselectivity constraints. Here we report a bio‐inspired iron catalyst bearing a cysteine‐derived ligand (BC t LOM) that enables radical hydroxyazidation of unconjugated tri‐, di‐, and monosubstituted alkenes with high anti‐Markovnikov selectivity. Utilizing TMSN 3 and hydrogen peroxide as azide source and oxidant, respectively, this method operates under mild conditions and tolerates diverse functional groups, including complex natural products and pharmaceuticals. Mechanistic studies suggest an iron‐oxo mediated radical pathway that suppresses competing epoxidation. This approach provides direct access to unprotected 2‐azido primary alcohols, versatile intermediates for further functionalization. The strategy expands the toolkit for selective alkene difunctionalization, offering potential applications in organic synthesis, chemical biology, and drug discovery.