一种方便有效地合成三烯酸与苯甲酸类化合物的方法

以烯酸炔丙基酯为反应原料,在碱性条件下,顺利发生分子内Ireland-Claisen重排/异构化反应,合成了标题化合物。实验结果表明,以乙腈作溶剂,在DBU(1,8-二氮双环[5.4.0]十一碳-7-烯)和TMSCl(三甲基氯硅烷)存在条件下,烯酸炔丙酯可顺利发生分子内重排反应,高收率地得到标题化合物,该合成路线具有反应条件温和、收率高等优点。

补骨脂酚的体外抗肿瘤活性及其关键中间体的合成研究

以他莫西芬为阳性对照物,考察了补骨脂酚的体外抗人乳腺癌细胞株生物活性。生物活性测试结果表明补骨脂酚在低剂量下即有抑制人乳腺癌细胞增殖作用,它对人乳腺癌细胞T-47D及MDA-MB-231的IC50分别为2.89×10-5mol·L-1及8.29×10-3mol·L-1。另一方面,本文以Ireland-Claisen重排为关键步骤,在合成补骨脂酚所需的关键中间体时,改进了常规Claisen重排反应的条件及试剂,避免了有毒试剂的使用。

Novel Concise Synthesis of （-）-Clausenamide1

A six-step synthesis of （-）-clausenamide is described. Optically pure （R,E）-1,3-diphenylallylic alcohol was ac-etylated and then subjected to an Ireland-Claisen rearrangement, giving the γ,δ-unsaturated acid, which underwent a substrate-induced stereoselective bromolactonization to afford the expected all-equatorial substituted bromo-δ-lac-one. An unusual chemo-selective aminolysis of the lactone resulted in the formation of a γ,δ-epoxy-amide in stereospecific manner. Base-promoted cyclization of this intermediate and the subsequent Davis oxidation furnished the synthesis, delivering the final product in 〉99% ee and up to 34% overall yield.