Institut für Organische Chemie, Universität Tübingen, Auf der Morgenstelle 18, 72076 Tübingen, Germany.
Org Lett. 2011 Aug 5;13(15):3940-3. doi: 10.1021/ol201464m. Epub 2011 Jun 27.
Starting from (R)-(-)-linalool (6), terminus differentiation and chain extension via aldol type reactions led to ketophosphonate 16 (C1-C8 building block). In a Horner-Wadsworth-Emmons reaction, 16 reacted with aldehyde 22, which contained the vicinal anti-Me-OH pattern and a vinyl iodide function, to provide the C1-C13 part of pladienolide B. After Shiina macrolactonization, reduction of the enone 26 gave the core structure 27. A Stille cross-coupling of vinyl iodide 27 with tributylphenylstannane eventually furnished analogue 30.
从（R）-（-）-芳樟醇（6）开始，通过醛醇型反应进行端基分化和链延伸，得到了酮膦酸酯 16（C1-C8 砌块）。在霍纳-沃兹沃思-埃蒙斯反应中，16 与醛 22 反应，22 含有顺式反-Me-OH 模式和乙烯基碘官能团，提供了 pladienolide B 的 C1-C13 部分。经过 Shiina 大环内酯化，烯酮 26 还原得到核心结构 27。三丁基苯锡烷与乙烯基碘化物 27 的 Stille 交叉偶联最终得到了类似物 30。
