The birth and development of pi-allylpalladium chemistry

The reaction of pi-allylpalladium chloride with malonate to give allylmalon ate discovered in 1965 marked the birth of pi-allylpalladium chemistry. A g roup of new synthetic reactions, developed subsequently in our laboratory b ased on Pd-catalyzed decarboxylation of allyl carbonates, allyl beta-keto c arboxylates, 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 ma lonates was developed by the introduction of the Pd-catalyzed reaction of t heir allylic esters. Hydrogenolysis of allylic compounds with triethylammon ium formate proceeds regio- and stereoselectively to afford regio- and ster eodefined olefins. The hydrogenolysis also can be used for deprotection of the allyl protecting group.