Total Synthesis of Farnesin through an Excited-State Nazarov Reaction
Total Synthesis of Farnesin through an Excited-State Nazarov Reaction
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激发态纳扎罗夫反应全合成法呢辛
DOI：
10.1002/anie.202001350
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发表时间：
2020
期刊：
影响因子：
--
通讯作者：
Gao Shuanhu
中科院分区：
文献类型：
--
作者：
Que Yonglei;Shao Hao;He Haibing;Gao Shuanhu
法呢素是一种具有代表性的贝壳杉烯类化合物，其不对称全合成是通过一种聚合方法实现的，该方法包括光-Nazarov环化和分子内羟醛醇环化，以构建syn-syn-synhydrofluorenol ABC环体系和双环[3.2.1]辛烷CD环体系，这是非芳香族双环二乙烯基酮的紫外光诱导激发态Nazarov环化在全合成中的首次应用。与传统的酸促进的基态Nazarov反应不同，激发态Nazarov反应能够通过对旋环化立体特异性地形成高度应变的顺-稠合氢芴酮支架。
The asymmetric total synthesis of farnesin, a rearrangedent‐kaurenoid, was achieved through a convergent approach involving photo‐Nazarov and intramolecular aldol cyclizations to build thesyn‐syn‐synhydrofluorenol ABC ring system and bicyclo[3.2.1]octane CD ring system in the first application of a UV‐light‐induced excited‐state Nazarov cyclization of a non‐aromatic dicyclic divinyl ketone in a total synthesis. Unlike the conventional acid‐promoted ground‐state Nazarov reaction, the excited‐state Nazarov reaction enables stereospecific formation of the highly strainedsyn‐syn‐syn‐fused hydrofluorenone scaffold through a disrotatory cyclization.