Following reactions of various allylic compounds catalyzed by palladium-phosphine complexes are surveyed. Allyl carbonates react with nucleophiles under neutral conditions at room temperature. Allyl alkenyl carbonates and allyl β-keto esters undergo decarboxylation and regioselective intramolecular allylation to afford allylated ketones. 1, 3-Dienemonoxides react with nucleophiles to give 1, 4-adduct with high selectivity. Palladium-catalyzed cyclization of methyl (
E) - 3-oxo-8-phenoxy-6-octenoate gives 3-vinylcyclopentanone-2-carboxylate, which is useful starting material for steroids and jasmonate syntheses. Allyl alkenyl carbonates and allyl β-keto esters are converted to α, β-unsaturated ketones by decarboxylative dehydrogenation in acetonitrile using diphosphine. Allylic compounds are converted to mainly 1-olefins by hydrogenolysis with formates. Allyl carbonates are carbonylated under mild conditions to give β, γ-unsaturated esters. Conjugated dienes are formed from allylic compounds by palladium- catalyzed elimination reaction.
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