Total Synthesis of Oidiodendrolides and Related Norditerpene Dilactones from a Common Precursor: Metabolites CJ-14,445, LL-Z1271γ, Oidiolactones A, B, C, and D, and Nagilactone F

An efficient, high-yielding strategy has been developed for the asymmetric total synthesis of seven norditerpenoid dilactones known for their diverse biological properties. The three key steps employed to obtain a tricyclic lactone intermediate involved a Morita−Baylis−Hillman reaction, the stereocontrolled construction of a γ-lactone through bromolactonization, and an efficient catalytic Reformatsky-type reaction. Access to CJ-14,445, LL-Z1271γ, oidiolactones A, B, C, and D, and nagilactone F was possible from a common intermediate. Structures and stereochemistry were determined by X-ray analysis.本研究开发了一种高效且高产率的策略，用于七种具有多样生物活性的去甲二萜双内酯（norditerpenoid dilactones）的不对称全合成。用于制备三环内酯中间体的三个关键步骤涵盖莫里塔-贝利斯-希尔曼（Morita−Baylis−Hillman）反应、通过溴代内酯化实现的γ-内酯立体控制构建，以及一种高效的催化型瑞福马茨基（Reformatsky）反应。以该通用中间体为原料，即可合成CJ-14,445、LL-Z1271γ、oidiolactones A、B、C、D以及nagilactone F。所有产物的结构与立体化学构型均通过X射线晶体衍射分析得以确证。