Activation of C-O and C-N bonds in allylic alcohols and amines by palladium complexes promoted by CO2. Synthetic applications to allylation of nucleophiles, carbonylation, and allylamine disproportionation

The direct activation of the C-O bonds in allylic alcohols catalyzed by palladium complexes has been accelerated by carrying out the reactions under CO2. On reaction with diethylamine, allyl alcohol can be converted into N,N-diethylallylamine in the presence of palladium complexes at room temperature under normal pressure of carbon dioxide. Allylation of various carbon nucleophiles such as beta-keto esters and beta-diketones can be achieved by using allylic alcohols directly in the presence of palladium complexes and CO2. Direct carbonylation of allylic alcohols into unsaturated carboxylic acids can be catalyzed by palladium complexes under the pressure of CO and CO2. Disproportionation of diallylamine into triallylamine and allylamine is also catalyzed by palladium complexes in the presence of CO2. On the basis of studies on the behavior of eta(3)-allylpalladium hydrogencarbonate complexes with the nucleophiles, mechanisms are proposed to account for the palladium-catalyzed allylation processes influenced by CO2.