Development of β-keto ester and malonate chemistry -: Palladium-catalyzed new reactions of their allylic esters

During extensive studies on pi-allylpalladium chemistry, we have developed classical beta-keto ester and malonate chemistry to a new generation by discovering a variety of palladium-catalyzed reactions of their allylic esters. Palladium enolates are generated from allyl beta-keto esters after decarboxylation and undergo the following transformations; a) reductive elimination to provide alpha-allyl ketones, b) elimination of beta-hydrogen to give alpha,beta-unsaturated ketones, c) formation of alpha-methylene ketones, d) hydrogenolysis to give ketones, e) aldol condensation, and f) Michael addition. Allyl malonates and cyanoacetes undergo similar reactions. Results of these studies, including several applications carried out by other researchers are summarized.