A convergent synthetic entry to the squalenoid polyether system has been developed and applied to the biologically active marine natural products thyrsiferyl 23-acetate (1a), thyrsiferol (1b), thyrsiferyl 18-acetate (1c), and thyrsiferyl 18,23-diacetate (1d). This involved the separate construction of two advanced intermediates representing the C1−C15 (4) and C16−C24 (5) domains, followed by their organochromium-mediated coupling, installation of the tertiary alcohol at C15, and manipulation of the C18 and C23 acetate moieties. The C1−C15 (4) intermediate containing the three tetrahydropyranyl rings (A−B−C) was derived from two preconstructed tetrahydropyran-containing units representing the functionalized A (C2−C6) and C (C10−C14) rings (6 and 7, respectively). The bromotetrahydropyranyl A ring was obtained via bromoetherification of the hydroxyalkene 16, which was synthesized from (2R,3R)-epoxy geraniol. The C ring was stereoselectively constructed by acid-catalyzed opening of the hydroxy epoxide 32, de...

中文翻译：

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Thyrsiferyl 23-Acetate 的全合成，一种蛋白磷酸酶 2A 的特异性抑制剂和一种抗白血病细胞凋亡诱导剂

已经开发了一种角鲨烯聚醚系统的收敛合成入口，并应用于具有生物活性的海洋天然产物 thyrsiferyl 23-acetate (1a)、thyrsiferol (1b)、thyrsiferyl 18-acetate (1c) 和 thyrsiferyl 18,23-diacetate（ 1d)。这涉及分别构建代表 C1-C15 (4) 和 C16-C24 (5) 域的两个高级中间体，然后是它们的有机铬介导的偶联，在 C15 上安装叔醇，以及对 C18 和 C23 乙酸盐的操作部分。包含三个四氢吡喃环 (A-B-C) 的 C1-C15 (4) 中间体衍生自两个预构建的包含四氢吡喃的单元，代表功能化的 A (C2-C6) 和 C (C10-C14) 环（6 和 7 ， 分别）。溴四氢吡喃基 A 环是通过羟基烯烃 16 的溴醚化获得的，羟基烯烃 16 由 (2R,3R)-环氧香叶醇合成。C环是通过羟基环氧化物32的酸催化开环立体选择性构建的，去...