Studies on Highly Stereoselective Synthetic Process Based on Palladium-Catalyzed Reactions for Biologically Active Compounds

1. 我们通过钯催化乙酰氧基甲基烯丙基- < β - > -酮羧酸酯的脱羧-去乙酰氧基化，建立了具有重要生物活性的功能基团< α - > -亚甲基酮和内酯的合成方法。我们还发现了几种钯催化丙炔化合物的反应。采用Sharpless环氧化法制备[Z，Z(22S,23R)]-烯氧化物，经钯催化的syn- <S_N> 2′环化，合成了具有光学活性的氢茚酮作为维生素<D_3>的前体。通过钯催化的烯丙基化反应进行了丁烯基化反应，然后进行了甲酸氢解反应。钯催化甲基(3R)-甲氧基羰基氧基-(4E)-癸烯丙二酸酯及其(Z)-异构体环化分别为(3R)-烷基- < δ > -内酯和(3S)-内酯，观察到有效的手性转移。

1. We developed general synthetic methods for <alpha> -methylene ketones and lactones, important functional group for biologically activity, by the palladium-catalyzed decarboxylation-deacetoxylation of allyl acetoxymethyl- <beta> -keto carboxylates. We also found several palladium-catalyzed reactions of propargyl compounds.2. Optically active hydroindenone was synthesized as a precusor of vitamin <D_3> by palladium-catalyzed syn- <S_N> 2' cyclization of [Z,Z(22S,23R)]-ene oxide, prepared by Sharpless epoxidation. The formal butenylation was also carried out by palladium catalyzed allylation, followed by hydrogenolysis with formate.3. Efficient chirality transfer was observed in the palladium-catalyzed cyclization of the methyl (3R)-methoxycarbonyloxy-(4E)-decenyl malonate and its (Z)-isomer to the (3R)-alkyl- <delta> -lactone and (3S)-lactone respectively.