1,3-Dioxane Functionalized Pd-PEPPSI Catalyst for Direct Arylation of Heteroaromatics

•A series of 1,3-dioxane functionalized benzimidazolium salts and their Pd-PEPPSI complexes were prepared and characterized by 1H and 13C NMR, FTIR, and LC-MS spectroscopic techniques.•The catalytic activities of these complexes were tested for direct arylation of heteroaromatics with various aryl bromides.•The experimental results showed that the synthesized complexes used were active catalysts in the direct arylation reaction of heteroaromatics. A series of benzimidazolium salts (1a-d) and their Pd-PEPPSI complexes (pyridine-enhanced precatalyst preparation, stabilization, and initiation) (2a-d) were prepared to catalyze the direct arylation of heteroaromatics (2-acetylthiophene and 2-furaldehyde) with various aryl bromides. The structures of all isolated compounds were elucidated based on spectroscopic methods (1H and 13C NMR, FT-IR and LC-MS spectroscopy). Under optimized reaction conditions, C5-arylated products were obtained in moderate to excellent yields in the direct arylation of heteroaromatics.