Department of Chemistry, University of Adelaide, Adelaide, SA 5005, Australia.
Org Biomol Chem. 2022 Feb 23;20(8):1759-1768. doi: 10.1039/d2ob00074a.
Oxidative degradation and rearrangement of polycyclic polyprenylated acylphloroglucinols (PPAPs) has created diverse families of unique natural products that are attractive targets for biomimetic synthesis. Herein, we report a racemic synthesis of hyperibrin A and its oxidative radical cyclization to give yezo'otogirin C, followed by epoxidation and House-Meinwald rearrangement to give hypermogin D. We also investigated the biomimetic synthesis of norascyronone A a similar radical cyclization pathway, with unexpected results that give insight into its biosynthesis.
多环聚异戊烯基酰基间苯三酚（PPAPs）的氧化降解和重排产生了多种多样的独特天然产物家族，这些产物是仿生合成的有吸引力的目标。在此，我们报告了海兔毒素 A 的外消旋合成及其氧化自由基环化得到的岩沙海葵毒素 C，接着进行环氧化和豪斯-迈因沃德重排得到的海兔毒素 D。我们还研究了类似的自由基环化途径的诺卡酮 A 的仿生合成，得到了意想不到的结果，这为其生物合成提供了深入的了解。
