Department of Chemistry, The University of Adelaide, Adelaide, SA 5005, Australia.
J Am Chem Soc. 2022 Dec 21;144(50):22844-22849. doi: 10.1021/jacs.2c09978. Epub 2022 Dec 12.
Inspired by a new biosynthetic hypothesis, we report a biomimetic total synthesis of atrachinenins A and B that explains their racemic nature. The synthesis exploits an intermolecular Diels-Alder reaction between a quinone meroterpenoid and -β-ocimene, followed by intramolecular (3 + 2) cycloaddition and a late-stage aerobic oxidation. Divergent transformations of a simple model system gave several complex polycyclic scaffolds, while also suggesting a structure revision for atrachinenin C.
受新的生物合成假说的启发，我们报告了阿特拉津宁 A 和 B 的仿生全合成，这解释了它们外消旋的性质。该合成利用了醌类杂萜和 -β-罗勒烯之间的分子间 Diels-Alder 反应，接着是分子内（3 + 2）环加成和后期的有氧氧化。一个简单模型系统的发散转化产生了几个复杂的多环支架，同时也对阿特拉津宁 C 的结构进行了修订。
