Acylsilanes for Palladium-Catalyzed Reversed-Polarity Synthesis of Diaryl Ketones

Diaryl ketones are versatile building blocks widely utilized in pharmaceuticals, materials science, and synthetic chemistry. Due to their structural importance and utility, many synthetic studies have been reported. Traditionally, diaryl ketones have been prepared via Friedel–Crafts acylation, even though this method suffers from limited functional group tolerance under acidic conditions. More recently, transition-metal catalyzed strategies have emerged, typically involving the coupling between carbonyl electrophiles and organometallics. As an alternative, we report the reversed-polarity synthesis of diaryl ketones using acylsilanes as carbonyl nucleophilic coupling partners in the presence of palladium catalyst. Inspired by our previous work on the synthesis of imines using imidoylsilanes, diaryliodonium salts were chosen as electrophilic partners. During optimization, the use of CsF was found to be essential, likely due to fluoride-mediated activation of acylsilanes and facilitation of the transmetalation. Various functionalized diaryl ketones, including more complex derivatives bearing tetrahydrotetramethylnaphthalene (TMN) moieties, were successfully synthesized using this method, demonstrating the synthetic utility.