Meyer A S, Hanzmann E, Murphy R C
Proc Natl Acad Sci U S A. 1971 Sep;68(9):2312-5. doi: 10.1073/pnas.68.9.2312.
The absolute configuration of the predominant Cecropia hormone, methyl 12,14-dihomojuvenate, has been determined to be methyl (E,E)-(10R,11S)-(+)-10,11-epoxy-7-ethyl-3,11-dimethyl-2, 6-tridecadienoate (I). The less abundant hormone, methyl 12-homojuvenate, can be presumed by analogy to have the corresponding 3,7,11-trimethyldienoate structure (II). The assignment has been established with microamounts of substance by applying Horeau's method to the glycol derivative (III) of the hormone.The course of the perchloric acid-catalyzed epoxide ring opening of I was checked by conducting the conversion in (18)O-labeled water. It has been ascertained that the configuration at the secondary hydroxyl group of the resulting III remained unchanged. On the other hand, the hydration proceeded with a surprisingly high rate of cis opening.
主要的塞克罗皮娅激素12,14 -二高保幼激素甲酯的绝对构型已确定为甲基(E,E)-(10R,11S)-(+)-10,11 -环氧-7 -乙基-3,11 -二甲基-2,6 -十三碳二烯酸酯（I）。含量较少的激素12 -高保幼激素甲酯，可以类推假定具有相应的3,7,11 -三甲基二烯酸酯结构（II）。通过将霍罗方法应用于该激素的二醇衍生物（III），已用微量物质确定了构型。通过在(18)O标记的水中进行转化，检查了高氯酸催化的I的环氧环开环过程。已确定所得III的仲羟基处的构型保持不变。另一方面，水合反应以惊人的高顺式开环速率进行。
