Department of Chemistry, The University of Adelaide, Adelaide, SA 5005, Australia.
Angew Chem Int Ed Engl. 2022 Aug 22;61(34):e202203311. doi: 10.1002/anie.202203311. Epub 2022 Jul 14.
Structurally unique natural products pose biosynthetic puzzles whose solution can inspire new chemical reactions. Herein, we propose a unified biosynthetic pathway towards some complex meroterpenoids-the hyperireflexolides, biyoulactones, hybeanones and hypermonones. This hypothesis led to the discovery of uncatalyzed, intramolecular carbonyl-ene reactions that are spontaneous at room temperature. We also developed an anionic cascade reaction featuring an α-hydroxy-β-diketone rearrangement and an intramolecular aldol reaction to access four distinct natural product scaffolds from a common intermediate.
结构独特的天然产物带来了生物合成谜题，其解决方案可以激发新的化学反应。在此，我们提出了一个统一的生物合成途径，用于合成一些复杂的混合萜类化合物——hyperireflexolides、biyoulactones、hybeanones 和 hypermonones。这一假设导致了室温下无需催化剂的分子内羰基-ene 反应的发现。我们还开发了一种阴离子级联反应，其特征在于α-羟基-β-二酮重排和分子内羟醛反应，从而从一个共同的中间体中获得四个不同的天然产物支架。
