Photocatalytic and Copper-Catalyzed 1,3-Aminoarylation of Aryl Cyclopropanes: Complementary Mechanistic Strategies for Synthesizing 3,3‑Diarylpropylamines

A regioselective 1,3-aminoarylation of aryl cyclopropanes is reported through two complementary catalytic strategies based on distinct reactivity. First, photoactivation of N-chloro-N-(phenylsulfonyl)benzenesulfonamide (NCBSI) enables a rapid and efficient 1,3-aminochlorination of aryl cyclopropanes. This transformation could be combined with a Friedel–Crafts arylation in a two-step, one-pot sequence, affording the corresponding arylated products bearing electron-rich arenes. Second, a copper-catalyzed protocol was developed, allowing direct 1,3-aminoarylation using electron-deficient aryl boronic acids as coupling partners. Mechanistic studies provide insight into the distinct reaction pathways underlying these complementary approaches. Together, these methodologies display broad functional group tolerance and provide access to 3,3-diarylpropylamines, valuable medicinally relevant motifs, in a one-pot process involving both C–N and C–C bond formation.