Merging of Two Photoredox Cycles with One Perovskite Catalyst Achieving Dual Functionalization: N-Heterocyclization and Site-Selective Bromination of N-Arylamines

Dual functionalization in organic synthesis represents a powerful strategy aimed at achieving multiple transformations within a single reaction cycle, thereby streamlining synthetic processes, enhancing efficiency, and imparting economic paths for complex molecules. Here, we report a heterogeneous perovskite nanocrystal (NC) photocatalytic system that can simultaneously drive two photoredox cycles in a single reaction. The dual process incorporates two distinct functional groups (N-heterocycles and bromines) into N-arylamines under the influence of a single catalyst (CsPbBr₃ NCs), allowing for the concurrent formation of two distinct architectures of 3-bromo-N-arylindoles. Mechanistically, long-lived charge separation and charge carrier accumulation at the NC surface enable perovskite to drive these two photoredox cycles simultaneously. The dual approach exploits light-induced holes to drive an amine oxidation in one cycle (I) and cooperatively utilizes dibromomethane (CH₂Br₂), a solvent-grade mild reagent for site-selective bromination, to achieve the other photoredox cycle (II). We find that chiral perovskite induces enantioselective axial C-N bond formation, but is inactive for axial C-C bond formation of arylindoles. Merging two photoredox cycles simultaneously to achieve dual functionalization is rare; thus, the perovskite NC photocatalysis not only aligns with the principles of green chemistry but also holds immense potential for the rapid and economical design of complex molecules.