Inspired by the proposed biogenic skeletal diversification process, the divergent total syntheses of 10 structurally complex pallavicinia diterpenoids with three distinct carbon skeletons, pallavicinin, neopallavicinin, pallambins A–D, pallaviambins A/B, and pallavicinolides B/C, were accomplished. Among them, the total syntheses of pallaviambins A/B and pallavicinolides B/C were achieved for the first time, and the synthetic routes of pallavicinin, neopallavicinin, and pallambins A/B were the shortest. The total syntheses feature a stereoselective Ireland-Claisen rearrangement to construct the C10 quaternary carbon stereocenter, the 2-fluoroethyl vinyl ether used as a masked methyl ketone for the first time, a biomimetic C2–C8 aldol reaction to construct the pallavicinin skeleton, a biomimetic cascade reaction of C4–C8 aldol reaction/oxa-Michael addition/MeOH elimination for the synthesis of pallambins C/D, and the spontaneously intramolecular Diels-Alder reaction to generate the pallavicinolide skeleton.

受所提出的生物骨骼多样化过程的启发，完成了 10 种结构复杂的 pallavicinia 二萜类化合物的不同全合成，这些二萜具有三种不同的碳骨架：pallavicinin、neopallavicinin、pallambins A-D、pallavinins A/B 和 pallavicinolides B/C。其中，首次实现了帕拉维霉素A/B和帕拉维霉素内酯B/C的全合成，且帕拉维霉素、新帕拉维霉素和帕拉维霉素A/B的合成路线最短。全合成包括立体选择性爱尔兰-克莱森重排构建C10季碳立构中心、首次用作掩蔽甲基酮的2-氟乙基乙烯基醚、仿生C2-C8羟醛反应构建仿生帕拉维星骨架C4-C8 羟醛反应/氧杂-迈克尔加成/MeOH 消除的级联反应用于合成 pallambins C/D，以及自发的分子内 Diels-Alder 反应生成 pallavicinolide 骨架。