Merging of Two Photoredox Cycles with One Perovskite Catalyst Achieving Dual Functionalization: N-Heterocyclization and Site-Selective Bromination of N-Arylamines
Year: 2025
Type: article
Abstract: 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 (CsPbBr 3 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 (CH 2 Br 2 ), 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.
Source: The Journal of Organic Chemistry
Authors: Kanchan Mishra, Isaac Hendrix, Jesse Gerardo, Nobuyuki Yamamoto, Yong Yan
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: green
Award: G3359591052
OpenAlex ID: W4408420767