The birth and development of π-allylpalladium chemistry

The reaction of pi-allylpalladium chloride with malonate to give allylmalonate discovered in 1965 marked the birth of pi-allylpalladium chemistry. A group of new synthetic reactions, developed subsequently in our laboratory based on Pd-catalyzed decarboxylation of allyl carbonates, allyl beta-keto carboxylates, and allyl formates are summarized. All these reactions proceed under neutral conditions. Allyl carbonates are very active for allylation of nucleophiles without a base. A new generation of beta-keto esters and malonates was developed by the introduction of the Pd-catalyzed reaction of their allylic esters. Hydrogenolysis of allylic compounds with triethylammonium formate proceeds regio- and stereoselectively to afford regio- and stereodefined olefins. The hydrogenolysis also can be used for deprotection of the allyl protecting group.