Total Synthesis and Structural Reassignment of (+/-)-Cereoanhydride
Total Synthesis and Structural Reassignment of (+/-)-Cereoanhydride
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(/-)-鲸蜡酸酐的全合成及结构重整
DOI：
10.1021/acs.orglett.6b02424
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发表时间：
2016
期刊：
影响因子：
5.2
通讯作者：
Hu Xiangdong
中科院分区：
文献类型：
--
作者：
Ren Zhiqiang;Hao Yu;Hu Xiangdong
在生物合成假说的启发下，首次实现了（±）-脑酸酐的全合成。提出的脑酸酐的生物合成前体trypethelone的三环骨架是由环丁烯酮的一个有趣的扩环一步构建的，其中引入的乙酰基是避免后续空气氧化的关键。在x射线晶体学分析的基础上，脑酸酐的结构被重新定位为螺旋结构2，该螺旋结构应该是由最初提出的结构异构化1形成的。
The first total synthesis of (±)-cereoanhydride has been achieved under the inspiration of its biosynthetic hypothesis. The tricyclic skeleton of trypethelone, the proposed biosynthetic precursor of cereoanhydride, was constructed by an interesting ring expansion of cyclobutenone in one step in which the introduced acetyl group is pivotal to avoid the following aerial oxidation. On the basis of X-ray crystallographic analysis, the structure of cereoanhydride is reassigned to a spiroketal structure2, which should be formed through an isomerization of the originally proposed structure1.