Iridium-Catalyzed Enantioselective Indole Cyclization: Application to the Total Synthesis and Absolute Stereochemical Assignment of (-)-AspidophyllineA
Iridium-Catalyzed Enantioselective Indole Cyclization: Application to the Total Synthesis and Absolute Stereochemical Assignment of (-)-AspidophyllineA
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DOI：
10.1002/anie.201511549
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发表时间：
2016-03-14
影响因子：
16.6
通讯作者：
Yang, Yu-Rong
中科院分区：
文献类型：
--
作者：
Jiang, Shi-Zhi;Zeng, Xue-Yi;Yang, Yu-Rong
首次完成了（-）-aspidophyllineA的对映选择性全合成，并确定了其绝对构型。合成的一个关键要素是一个高对映选择性吲哚烯丙基烷基化/亚胺鎓环化级联，这是通过采用刘易斯酸活化和铱/配体催化剂的组合开发的。该策略依赖于直接使用具有在C2处附加的仲烯丙醇和在C3处附加的杂亲核试剂的2，3-二取代的吲哚，吲哚容易在C-H活化条件下由简单的起始原料制备。
The first enantioselective total synthesis of (-)-aspidophyllineA, including assignment of its absolute configuration has been accomplished. A key element of the synthesis is a highly enantioselective indole allylic alkylation/iminium cyclization cascade which was developed by employing a combination of Lewis acid activation and an iridium/ligand catalyst. This strategy relies on the direct use of 2,3-disubstituted indoles with secondary allylic alcohols appended at C2 and heteronucleophiles appended at C3, indoles which are easily prepared from simple starting materials under C-H activation conditions.