Exploring the pivotal role of silver(I) additives in palladium-catalyzed NH2-directed C(sp3)–H arylation reactions

Combined theoretical and experimental studies have explained the mechanism of Pd-catalyzed δ-C(sp3)−H arylation of primary amines. Instead of the monomeric Pd mechanism, our research unveils that all steps including C–H activation, oxidative addition, and reductive elimination take place via the heterodimeric Pd–Ag intermediates and transition states. Experimentally, the active heterodimeric Pd–Ag species were detected by mass spectrometry, which further confirms the proposed heterodimeric mechanism. Insight gained through this study reveals the synergistic manner of palladium catalysis and silver(I) additives in native NH2-directed C‒H activation and C–C coupling reactions. The mechanism of Pd-catalyzed δ-C(sp3)−H arylation of amines has been explored by a computational and experimental study. Instead of the monomeric Pd mechanism, our research unveils that all steps including C–H activation, oxidative addition and reductive elimination take palce via the heterodimeric Pd–Ag pathway. [Display omitted]