Comprehensive Summary Transition‐metal‐catalyzed reductive coupling of unactivated alkenyl carbamates remains challenging due to the high bond dissociation energy of the C( sp 2 )–O bond. By designing a remote directing strategy based on noncovalent interactions involving aromatic π‐system, we herein report an iron‐catalyzed reductive cross‐coupling reaction that enables the efficient coupling of alkenyl carbamates derived from cyclohexene frameworks with alkyl bromides within an iron/diboron catalytic system. Mechanistic studies suggest that this transformation is facilitated by a C–H–π interaction between the pendant aryl moiety on the cyclohexene substrate and a C–H bond on the ligand, while an iron(I) species likely serving as the catalytically active intermediate. These findings provide insights into iron‐catalyzed activation of unactivated C( sp 2 )–O bonds and may open avenues for the development of transformations of other chemical bonds via remote directing strategies enabled by noncovalent interactions.
Bai et al. (Sun,) studied this question.