The photo-Nazarov reaction: scope and application.
The photo-Nazarov reaction: scope and application.
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DOI：
10.1002/chem.201402993
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发表时间：
2014-07
期刊：
影响因子：
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通讯作者：
S. Cai;Zheming Xiao;Yingbo Shi;Shuanhu Gao
中科院分区：
文献类型：
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作者：
S. Cai;Zheming Xiao;Yingbo Shi;Shuanhu Gao
研究了芳基乙烯基酮的光Nazarov反应的反应条件和反应范围。与传统的酸催化方法不同，这种光解电环化反应在中性或碱性条件下进行。用紫外光（254 nm）照射带有各种芳环、酸敏感基团、环己烯基、环庚烯基和不饱和吡喃的底物，顺利地产生六氢芴酮和相关结构。这种光Nazarov反应也适用于烯酮上带有β-烷基的底物，得到相应的含季中心的多环。这些光电环化产物可能有助于合成各种天然产物及其衍生物。进一步将该温和的光Nazarov反应应用于台湾醌醇B的合成。
The reaction conditions and scope of the photo-Nazarov reaction of aryl vinyl ketones were investigated. In contrast to the conventional acid-catalyzed methods, this photolytic electrocyclization proceeds in the neutral or basic conditions. Irradiating substrates bearing various aromatic rings, acid-sensitive groups, cyclohexenyl, cycloheptenyl, and unsaturated pyran with UV-light (254 nm) smoothly yielded hexahydrofluorenones and related structures. This photo-Nazarov reaction could also be applicable to the substrates carrying β-alkyl groups on the enone, which gave corresponding polycyclic rings containing quaternary centers. These photo-electrocyclized products may prove useful for synthesizing a variety of natural products and their derivatives. Further application of this mild photo-Nazarov reaction in the synthesis of taiwaniaquinol B was achieved.