摘要/Abstract
为了优化3-苯基-7-甲基-7-羟基-2-辛烯-6-内酯的化学结构, 通过环氧化-内酯化和Sharpless不对称双羟基化反应作为关键步骤, 分别以61%~91%的收率实现了消旋及光活性3-芳基-7-甲基-7-羟基-2-辛烯-6-内酯类化合物的合成, 其结构经过IR, 1H NMR, 13C NMR和HR-ESI-MS的表征. 对它们的杀菌活性进行了评价, 结果表明(R)-3-苯基-7-甲基-7-羟基-2-辛烯-6-内酯(5a)活性最好的化合物, 对6种植物病原菌的EC50值在0.2~13.5 µg/mL范围, 优于其( S)-异构体及消旋体混合物. 它可以作为先导结构进行进一步结构优化. 扫描电镜和透射电镜观测的结果显示, 化合物(S)-5a,5d和5j对油菜菌核菌菌丝细胞的结构和功能有显著影响.
关键词: 3-芳基-7-甲基-2-辛烯-6-内酯, 环氧化-内酯化反应, 不对称双羟基化反应, 杀菌活性
In order to optimize the structure of 3-phenyl-7-methyl-7-hydroxy-2-octen-6-olide, the synthesis of racemic and optical 3-aryl-7-methyl-7-hydroxy-2-octen-6-olides has been achieved via epoxidation-lactonization procedure and Sharpless asymmetric dihydroxylation as the key steps in 61%~91% yields, respectively. Their structures were fully characterized by IR, 1H NMR, 13C NMR, and HRMS data. Their antifungal activities were evaluated, and it showed that (R)-3-phenyl-7-methyl- 7-hydroxy-2-octen-6-olide (5a) was the most active compound with the EC 50 values in the range of 0.2~13.5 µg/mL against the tested six phytopathogens, better than its ( S)-isomer and racemic mixture. It would be the potential lead structure to be optimized. The scanning electron microscopy (SEM) and transmission electron microscopy (TEM) observation indicated that compounds (S)-5a, 5d and 5j had a significant impact on the structure and function of the hyphal cell wall of S. sclerotiorum mycelium.
Key words: 3-aryl-7-methyl-7-hydroxy-2-octen-6-olide, epoxidation-lactonization, asymmetric dihydroxylation, antifungal activity
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