ACS Catalysis, Journal Year: 2024, Volume and Issue: 15(1), P. 284 - 295

Published: Dec. 17, 2024

Buchwald–Hartwig (BH) aminations are crucial for synthesizing arylamine motifs in numerous bioactive molecules and fine chemicals. While homogeneous palladium complexes can be effective catalysts, their high costs environmental impact motivate the search alternative approaches. Heterogeneous single-atom catalysts (SAC) offer promising recoverable alternatives C–C cross-couplings. Yet use C–N couplings remains unexplored, mechanistic insights into amine coupling with aryl halides over solid surfaces that could guide catalyst design lacking. Here, we demonstrate atoms coordinated to well-defined heptazinic cavities of graphitic carbon nitride (Pd1@C3N4) deliver practically relevant yields BH across various amines, exhibiting persistent activity negligible leaching several cycles. Notably, Pd1@C3N4 shows comparable or superior certain chlorides bromides, alongside chemoselectivity amines amides. In situ X-ray absorption spectroscopy analyses supported by density functional theory simulations identify concerted role ligand C3N4 host determining performance, a Pd(II) nominal oxidation state observed under all conditions. Complementary structural kinetic studies highlight distinct reaction mechanism than typically reported catalysts. These findings key designing recyclable SAC coupling, setting basis extending scope toward more complex industrial targets.

Language: Английский