Total syntheses of HMP-Y1, hibarimicinone, and HMP-P1.
Total syntheses of HMP-Y1, hibarimicinone, and HMP-P1.
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DOI：
10.1021/ja307207q
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发表时间：
2012-10-10
影响因子：
15
通讯作者：
Shair, Matthew D.
中科院分区：
文献类型：
--
作者：
Liau, Brian B.;Milgram, Benjamin C.;Shair, Matthew D.
使用双向合成策略描述了 HMP-Y1、atrop-HMP-Y1、hibarimicinone、atrop-hibarimicinone 和 HMP-P1 的全合成。开发了一种新型的氟化苄迈克尔-克莱森反应序列，通过对称、双向、双环化构建 HMP-Y1 和 atrop-HMP-Y1 的完整碳骨架。通过将 HMP-Y1 衍生物转化为 hibarimicinone 和 HMP-P1，实现了仿生单氧化作用，使受保护的 HMP-Y1 去对称。开发了双向不对称双环化和仿生醚化来构建 hibarimicinone、atrop-hibarimicinone 和 HMP-P1 的多环和高氧化骨架。外消旋联芳基前体的使用允许合成两种hibarimicinone阻转异构体，并首次证实了atrop-hibarimicinone的结构。此外，这项工作首次报道了阿托品-hibarimicinone、HMP-Y1、atrop-HMP-Y1 和 HMP-P1 的完整表征。最后，发现了关于 hibarimicinone C2-C2' 键的 pH 依赖性旋转屏障，这为实现 hibarimicinone 糖基化同系物的合成提供了必要的有价值的信息。
Total syntheses of HMP-Y1, atrop-HMP-Y1, hibarimicinone, atrop-hibarimicinone, and HMP-P1 are described using a two-directional synthesis strategy. A novel benzyl fluoride Michael–Claisen reaction sequence was developed to construct the complete carbon skeleton of HMP-Y1 and atrop-HMP-Y1 via a symmetrical, two-directional, double annulation. Through efforts to convert HMP-Y1 derivatives to hibarimicinone and HMP-P1, a biomimetic mono-oxidation to desymmetrize protected HMP-Y1 was realized. A two-directional unsymmetrical double annulation and biomimetic etherification were developed to construct the polycyclic and highly-oxidized skeleton of hibarimicinone, atrop-hibarimicinone, and HMP-P1. The use of a racemic biaryl precursor allowed for the synthesis of both hibarimicinone atropisomers and provides the first confirmation of the structure of atrop-hibarimicinone. Additionally, this work documents the first reported full characterization of atrop-hibarimicinone, HMP-Y1, atrop-HMP-Y1, and HMP-P1. Lastly, a pH-dependent rotational barrier about the C2–C2' bond of hibarimicinone was discovered, which provides valuable information necessary to achieve syntheses of the glycosylated congeners of hibarimicinone.
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影响因子：
5.2
作者：
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通讯作者：
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