π-アリルパラジウム錯体を活性中間体とするアリル化合物の触媒的反応

抄録

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.