Palladium-Catalyzed Decarboxylation-Allylation of Allylic Esters of α-Substituted β-Keto Carboxylic, Malonic, Cyanoacetic, and Nitroacetic Acids

Article abstract of DOI:10.1021/jo00390a007

Decarboxylation-allylation of allylic β-keto carboxylates using Pd(OAc)2-PPh3 or Pd2(dba)3*CHCl3-dppe as a catalyst proceeds smoothly to give α-allylated ketones.The reaction is highly regioselective.In some cases, diallylated ketones are obtained with allylic esters bearing an active proton(s).Also rhodium, molybdenum, and nickel complexes sre active catalysts in this reaction.Similarly allylic esters of α-substituted malonates, cyanoacetates, and nitroacetate undergo the palladium-catalyzed decarboxylation-allylation to afford allylated acetate, acetonitrile, and nitromethane, respectively.The mechanisms of these palladium-cataly zed decarboxylation-allylations are discussed