Nitrogen compounds palladium-catalyzed allylation

This one-step transformation of an alkene to an allylic acetate compares well with other methods of preparation such as hydride reduction of a, 8-unsaturated carbonyl compounds followed by esterification. The scope and limitations of the reaction have been investigated. The allylic acetoxylation proceeds via a TT-allylpalladium intermediate, and as a result, substituted and linear alkenes generally give several isomeric allylic acetates. With oxygen nucleophiles the reaction is quite general, and reactants and products are stable towards the reaction conditions. This is normally not yet the case with nitrogen nucleophiles, although one intramolecular palladium-catalyzed allylic amination mechanistically related to allylic acetoxylation has been reported. ... [Pg.458]

Some synthetically useful isomerization reactions of alkenes, other than nitrogen- or oxygen-substituted allylic compounds, were reported by the use of a catalytic amount of transition metal complexes. The palladium complex, /ra r-Pd(C6HsCN)2Gl2, effectively catalyzed the stereoselective isomerization of /3,7-unsaturated esters to a,/3-unsaturated esters (Equation (26)). [Pg.93]