Organic Synthesis and Process Chemistry Division, CSIR-Indian Institute of Chemical Technology, Hyderabad-500007, India.
Org Biomol Chem. 2018 Nov 21;16(45):8810-8818. doi: 10.1039/c8ob02301h.
A concise synthetic strategy towards the core structure of (-)-apicularen A has been described in an 11-step synthetic sequence from a known intermediate. The key steps include tandem isomerization followed by C-O and C-C bond-forming reactions and iodocyclization strategies for the synthesis of a bicyclic ether embedded in the macrolactone ring. The applied reagent-controlled Keck-Maruoka allylation, Lin Pu alkynylation and Ricket-Diels-Alder reactions were used to simplify the synthetic sequence of related natural products. An intramolecular Yamaguchi lactonization constructed the macrolactone core, while the attempt to install the C11 hydroxyl chiral centre either under catalytic hydrogenation conditions or oxidative conditions was not successful.
描述了一种简洁的全合成策略，通过 11 步合成序列，从已知的中间体出发，构建 (-)-apicularen A 的核心结构。关键步骤包括串联异构化，随后进行 C-O 和 C-C 键形成反应，以及碘环化策略，用于合成大环内酯环中嵌入的双环醚。应用试剂控制的 Keck-Maruoka 烯丙基化、Lin Pu 炔基化和 Ricket-Diels-Alder 反应简化了相关天然产物的合成序列。分子内 Yamaguchi 内酯化构建了大环内酯核心，而尝试在催化氢化条件或氧化条件下引入 C11 羟基手性中心均未成功。
