著者
辻 二郎
出版者
公益社団法人精密工学会
雑誌
精密機械 (ISSN:03743543)
巻号頁・発行日
vol.26, no.304, 1960-05-05
著者
辻 二郎
出版者
The Society of Synthetic Organic Chemistry, Japan
雑誌
有機合成化学協会誌 (ISSN:00379980)
巻号頁・発行日
vol.41, no.7, pp.619-632, 1983-07-01 (Released:2009-11-13)
参考文献数
54
被引用文献数
9 8

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.