Iridium-Catalyzed Enantioselective Indole Cyclization: Application to the Total Synthesis and Absolute Stereochemical Assignment of (-)-AspidophyllineA

被引:125
作者
Jiang, Shi-Zhi [1 ]
Zeng, Xue-Yi [1 ,2 ]
Liang, Xiao [1 ,2 ]
Lei, Ting [1 ]
Wei, Kun [1 ]
Yang, Yu-Rong [1 ]
机构
[1] Chinese Acad Sci, Kunming Inst Bot, State Key Lab Phytochem & Plant Resources West Ch, Lanhei 132, Kunming 650201, Peoples R China
[2] Univ Chinese Acad Sci, Beijing 100039, Peoples R China
关键词
cyclizations; enantioselectivity; indoles; iridium; total synthesis; ALLYLIC DEAROMATIZATION REACTION; AKUAMMILINE ALKALOIDS; STRYCHNOS ALKALOIDS; ENOL ETHERS; ALLYLATION; ALKYLATION; ALCOHOLS; (+/-)-NORFLUOROCURARINE; FUNCTIONALIZATION; (+/-)-AKUAMMICINE;
D O I
10.1002/anie.201511549
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
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.
引用
收藏
页码:4044 / 4048
页数:5
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