Ketyl Radical Generation by Photoexcited Palladium and Development of Organopalladium-Type Reactions

Enabling reactions of traditional substrates that are inert to Pd catalysts has the potential for further advancements in the field of Pd chemistry. In this study, we developed a method for generating ketyl radicals through the reaction of a photoexcited Pd species with ketones. Upon subsequent reaction with olefins, the ketyl radicals generated through this method yielded Pd-specific reductive and Heck-type coupling products. Mechanistic studies indicated that the proposed radical generation method exhibits characteristics distinct from those of traditional methods such as SmI2 reduction and photoredox-catalyzed reactions.