An eight-step synthesis of epicolactone reveals its biosynthetic origin
An eight-step synthesis of epicolactone reveals its biosynthetic origin
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DOI：
10.1038/nchem.2336
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发表时间：
2015-11-01
期刊：
影响因子：
21.8
通讯作者：
Trauner, Dirk
中科院分区：
文献类型：
--
作者：
Ellerbrock, Pascal;Armanino, Nicolas;Trauner, Dirk
表内酯是最近分离的真菌代谢产物，其大小非常复杂，但仍是外消旋的。由于其四级立体中心阵列，高度官能化和复杂的多环结构，它对合成构成了相当大的挑战，这一挑战可以通过了解其生物合成来源来应对。如果以某种方式绘制，epicolactone揭示了一种类似于purpurogallin的模式，purpurogallin是通过氧化二聚形成的普遍存在的天然着色剂的原型。基于这一认识，我们设计了一种从香草醇出发，仅需八步即可合成表内酯的仿生合成方法。我们已经分离出一个关键的中间体，支持我们的生物合成假设，并预计，异构体的epicolactone源于我们的合成努力也可以被发现作为一种天然产物。
Epicolactone is a recently isolated fungal metabolite that is highly complex for its size, and yet racemic. With its array of quaternary stereocentres, high degree of functionalization and intricate polycyclic structure, it poses a considerable challenge to synthesis, a challenge that can be met by understanding its biosynthetic origin. If drawn in a certain way, epicolactone reveals a pattern that resembles purpurogallin, the archetype of ubiquitous natural colourants formed via oxidative dimerization. Based on this insight, we designed a biomimetic synthesis of epicolactone that proceeds in only eight steps from vanillyl alcohol. We have isolated a key intermediate that supports our biosynthetic hypothesis and anticipate that an isomer of epicolactone stemming from our synthetic efforts could also be found as a natural product.