Divergent approach to the bisanthraquinone natural products: total synthesis of (S)-bisoranjidiol and derivatives from binaphtho-para-quinones.
Divergent approach to the bisanthraquinone natural products: total synthesis of (S)-bisoranjidiol and derivatives from binaphtho-para-quinones.
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双蒽醌天然产物的不同方法：(S)-双索兰基二醇和联萘对醌衍生物的全合成。
DOI：
10.1021/jo302364h
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发表时间：
2013
期刊：
影响因子：
--
通讯作者：
Kozlowski,MarisaC
中科院分区：
文献类型：
--
作者：
Podlesny,ErinE;Kozlowski,MarisaC
概述了手性蒽醌二聚体的首次不对称合成的进展，从而实现了 (S)-双索兰吉二醇的首次全合成。蒽基环系统不是仿生二聚逆合成断开，而是在轴向手性联萘骨架形成后生成。这种合成策略使得多种类似物的合成成为可能。该合成的关键特征包括在 C-C 键形成位点上含有取代基的受阻 2-萘酚的对映选择性偶联、8,8'-羟基化联萘酚区域选择性氧化为联萘对醌，以及串联区域选择性 Diels-Alder/芳构化反应。
The development of the first asymmetric synthesis of a chiral anthraquinone dimer is outlined, resulting in the first total synthesis of (S)-bisoranjidiol. Rather than a biomimetic dimerization retrosynthetic disconnection, the anthracenyl ring systems are generated after formation of the axially chiral binaphthalene framework. This synthetic strategy has enabled the synthesis of several analogues. Key features of the synthesis include the enantioselective coupling of a hindered 2-naphthol containing substitutionperito the site of C–C bond formation, the regioselective oxidation of 8,8′-hydroxylated binaphthols to binaphtho-para-quinones, and a tandem regioselective Diels–Alder/aromatization reaction.