Formal Total Synthesis of (+)-Diepoxin σ
Formal Total Synthesis of (+)-Diepoxin σ
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DOI：
10.1021/jo000684t
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发表时间：
2000-09
影响因子：
3.6
通讯作者：
P. Wipf;Jae-Kyu Jung
中科院分区：
文献类型：
--
作者：
P. Wipf;Jae-Kyu Jung
以O-甲基萘扎林为原料，经10步反应合成了高氧抗真菌抗癌天然产物（+/-）-二环氧辛σ，总收率15%。的合成工作的亮点包括乌尔曼耦合和可能的仿生氧化螺环化的萘缩酮的引入，以及使用的逆Diels-桤木反应，揭露反应性烯酮部分的萘醌bisepoxide环系统。开发了一种新型的大体积手性联萘并环配体，用于硼介导的Diels-Alder反应，该反应构成了（+）-二环氧辛σ的形式不对称全合成。
The highly oxygenated antifungal anticancer natural product (+/-)-diepoxin sigma was prepared in 10 steps and in 15% overall yield from O-methylnaphthazarin. Highlights of the synthetic work include an Ullmann coupling and a possibly biomimetic oxidative spirocyclization for the introduction of the naphthalene ketal as well as the use of a retro-Diels-Alder reaction to unmask the reactive enone moiety in the naphthoquinone bisepoxide ring system. A novel highly bulky chiral binaphthol ligand was developed for a boron-mediated Diels-Alder reaction that constitutes a formal asymmetric total synthesis of (+)-diepoxin sigma.