Eremophilane sesquiterpenes from capsidiol.
Eremophilane sesquiterpenes from capsidiol.
复制标题
DOI：
10.1021/jo049058c
复制
发表时间：
2004-10
期刊：
影响因子：
--
通讯作者：
Yuxin Zhao;D. Schenk;Shunji Takahashi;J. Chappell;R. Coates
中科院分区：
文献类型：
--
作者：
Yuxin Zhao;D. Schenk;Shunji Takahashi;J. Chappell;R. Coates
以植物保鲜蛋白Capsidiol(1)为原料，制备了一系列马兜铃烯倍半萜醇和烃类化合物，用于表马兜铃烯合成酶和表马兜铃烯二羟基酶的机理研究。其中，3-脱氧羟基(10)是通过赤道3α羟基的选择性衍生化和还原裂解得到的。从1-和3-脱氧戊二醇异构体中得到马兜铃烯和马兜铃烯两种新的异构体。表马兜铃烯-1-酮对甲苯磺酰肼经儿茶酚硼烷共轭还原、亚磺酸盐消除和二亚胺重排反应制得4-表马兜铃烯(17)。表马兜铃烯-3-酮(27A)在C4甲基上的表异构化，然后还原，得到了以前未知的马兜铃烯异构体-9(10)，11(12)-二烯(30)。旋光度和特征(1)相关的马钱子醇和双烯的核磁共振数据在表1和表2中收集。最后，使用生物测定来评估卡西二醇及其合成衍生物的抗真菌能力。Capsidiol(3-10 ng)的最小抑菌浓度比任何一种衍生物至少低一个数量级，比已报道的酮康唑、制霉菌素和丙环唑低很多。
A series of eremophilane sesquiterpene alcohols and hydrocarbons was prepared from the phytoalexin capsidiol (1) for mechanistic studies with epiaristolochene synthase and epiaristolochene dihydroxylase. Among them, 3-deoxycapsidiol (10) was obtained through selective derivatization and reductive cleavage of the equatorial 3 alpha hydroxyl group. Two novel isomers of aristolochene and eremophilene were accessed from the 1- and 3-deoxycapsidiol isomers. 4-Epieremophilene (17) was obtained by conjugate reduction of epiaristolochen-1-one tosylhydrazone with catecholborane followed by sulfinate elimination and diimide rearrangement. Epimerization of epiaristolochen-3-one (27a) at the C4 methyl followed by reductions led to the previously unknown aristolochene isomer, eremophila-9(10),11(12)-diene (30). Optical rotations and characteristic (1)H NMR data for the related eremophilenols and dienes are collected in Tables 1 and 2. Finally, bioassays were used to assess the antifungal potencies of capsidiol and its synthetic derivatives. The minimum inhibitory concentration for capsidiol (3-10 ng) was at least 1 order of magnitude lower than that of any of the derivatives and considerably lower than those previously reported for ketoconazole, nystatin, and propiconazole.