Shenzhen Grubbs Institute, Department of Chemistry, Southern University of Science and Technology, Shenzhen 518055, China.
J Am Chem Soc. 2022 Jun 15;144(23):10162-10167. doi: 10.1021/jacs.2c04633. Epub 2022 Jun 3.
The first asymmetric total synthesis of bioactive diterpenoid hypoestin A with an unprecedented [5-8-5-3] tetracyclic skeleton is accomplished in 15 steps from commercially available ()-limonene. Furthermore, the second asymmetric total syntheses of sesterterpenoids albolic acid and ceroplastol II in 21 steps are also reported. The synthetically challenging and highly functionalized [-8-5] ( = 5 or 7) tricarbocyclic ring systems found in hypoestin A, albolic acid, ceroplastol II, and schindilactone A, as well as other natural products, are efficiently and directly constructed via a unique intramolecular Pauson-Khand reaction of an allene-yne. This work represents the first reported use of the Pauson-Khand reaction to access synthetically challenging eight-membered-ring systems in natural product synthesis.
具有空前 [5-8-5-3] 四环骨架的生物活性二萜类hypoestin A 的首次不对称全合成是从商业可得的（）-柠檬烯经 15 步完成的。此外，还报道了二萜类化合物 albolic acid 和 ceroplastol II 的第二个不对称全合成，总步数为 21 步。在 hypoestin A、albolic acid、ceroplastol II 和 schindilactone A 以及其他天然产物中发现的合成极具挑战性且高度官能化的 [-8-5]（=5 或 7）三环碳环系统是通过独特的烯炔的分子内 Pauson-Khand 反应有效地和直接构建的。这项工作代表了 Pauson-Khand 反应在天然产物合成中首次用于构建具有挑战性的八元环系统的报道。
