Exploitation of Chiral Epichlorohydrin as Versatile Chiral Building Block

我国通过发酵法实际得到了对映体纯的环氧氯丙烷。为了利用对映体纯环氧氯丙烷作为多用途手性构建块，我们研究了多种生理活性天然产物的对映体控制构建，包括氨基酸、生物碱、聚酮、萜烯和类固醇。在1995-1997年期间，我们一直从事对对体控制合成“Sporochnol a”，来自加勒比海洋藻类的鱼类威慑物，“carbazoquinocins a和D”，来自紫链霉菌2248-SVT2的强效脂质过氧化抑制剂，“紧实蛋白内酯”，与强效HMG-CoA还原酶紧实蛋白的生物活性相关的基本结构成分，“骨化三醇烯”，维生素D活性形式的a环成分，“二羟基heliotridane”，一种生理上有趣的necine碱，以及“muscarine和三种天然产生的非对映体”，蘑菇毒素显示出强大的抗胆碱能活性。其中，孢霉醇A、咔唑喹啉A和D的绝对构型与原料环氧氯丙烷的绝对构型进行了对比。

Epichlorohydrin was obtained practically in enantiomerically pure forms by fermentation in our country. In order to exploit enantiomerically pure epichlorohydrin as versatile chiral building block, we have investigated enantiocontrolled construction of a variety of physiologically active natural products including amino acids, alkaloids, polyketides, terpenes, and steroids. During a 1995-1997 period, we have been engaged in the enantiocontrolled syntheses of "Sporochnol A", the fish deterrent from the Caribbean Marine alge, "carbazoquinocins A and D", the potent lipid peroxidation inhibitors from Streptomyces violaceus 2248-SVT2, "compactin lactone", the essential structural component associated with the biological activity of the potent HMG-CoA reductase compactin, "calcitriol enyne", the a ring component of the activated form of vitamin D,"dihydroxyheliotridane", a physiologically interesting necine base, and "muscarine and three naturally occurring its diastereomers", mushroom poisons exhibiting potent anticholinergic activity. Among these compounds obtained, the absolute configurations of sporochnol A,carbazoquinocins A and D were determined by these syntheses by correlation to the absolute configuration of epichlorohydrin used as the starting material.