Modular synthesis of 3,3-diarylpropylamines via the photo- and copper-catalyzed 1,3-aminoarylation of cyclopropanes

3,3-Diarylpropylamines are privileged pharmacophores in drugs such as fendiline and tolterodine, but their synthesis has been limited by the use of stepwise, single-bond-forming routes. We report the first 1,3-aminoarylation of the C–C bond in aryl cyclopropanes, achieved through two mechanistically distinct, complementary catalytic transformations. The photoactivation of N-chloro-N-(phenylsulfonyl)benzenesulfonamide (NCBSI) gives regioselective 1,3-aminochlorination; the resulting chloroamine is further elaborated by Friedel–Crafts coupling with electron-rich arenes or telescoped reductive coupling with aryl iodides to give the 1,3-aminoarylation products. A copper-catalyzed process instead couples electron-poor aryl boronic acids, N-fluoro-N-(phenylsulfonyl)benzenesulfonamide (NFSI) and aryl cyclopropanes in a single step. Collectively, these approaches give access to aryl partners spanning the full electronic spectrum, enabling the modular and convergent synthesis of structurally diverse 3,3-diarylpropylamines from a common cyclopropane precursor.