Synthesis of Benzopyran Atropisomers via Electrophilic Halogenation

We report a halogenation‐based strategy for the synthesis of axially chiral benzopyrans, a rare and underexplored class of nonbiaryl atropisomers. The reaction exhibits broad substrate scope, tolerating both electron‐donating and electron‐withdrawing substituents, and accommodates the incorporation of bromine, chlorine, and iodine. A sequential double bromination enables the construction of bisbenzopyrans bearing two stereogenic axes. Preliminary enantioselective brominations catalyzed by chiral phosphoric acids delivered enantiomeric excesses of up to 56%. The method was successfully scaled to gram level and further elaborated through Suzuki coupling, highlighting its synthetic versatility. This work provides a new platform for the atroposelective synthesis of benzopyran‐based architectures.