文献类型：期刊文献

英文题名：Catalytic asymmetric dipolar cycloadditions of indolyl delocalized metal-allyl species for the enantioselective synthesis of cyclopenta [b]indoles and pyrrolo[1,2-a]indoles

作者：Tian, Fei[1,2];Yang, Wu-Lin[1,2];Ni, Tao[1,2];Zhang, Jian[1,2];Deng, Wei-Ping[1,2]

机构：[1]East China Univ Sci & Technol, Shanghai Key Lab New Drug Design, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Sch Pharm, Shanghai 200237, Peoples R China

年份：2021

卷号：64

期号：1

起止页码：34

外文期刊名：SCIENCE CHINA-CHEMISTRY

收录：;EI(收录号：20204409411745);WOS:【SCI-EXPANDED(收录号:WOS:000582405600001)】；

基金：This work was supported by the National Natural Science Foundation of China (21901072), the China Postdoctoral Science Foundation (2019T120310) and Shanghai Sailing Program (18YF140560). Prof. Ying-Chun Chen of Sichuan University is acknowledged for helpful discussions. The authors thank the Research Center of Analysis and Test of East China University of Science and Technology for the assistance with the HRMS and NMR analyses.

语种：英文

外文关键词：palladium catalysis; iridium catalysis; asymmetric synthesis; dipolar cycloaddition; polycyclic indoles

摘要：The development of novel synthons and efficient methods to synthesize chiral polycyclic indoles has been a hot topic in organic synthesis and medicinal chemistry owing to their broad applications in medicines, pesticides, and other functional molecules. Here, we disclosed novel indolyl substituted metal-allyl zwitterionic intermediates through the decarboxylation of conveniently available vinyl indoloxazolidones, which could be regarded as two types of dipolar species through the anionic delocalization. The palladium-pi-allyl species tended to serve as an all-carbon 1,3-dipole in the asymmetric [3+2] cycloaddition with electron-deficient alkenes, which furnished polysubstituted cyclopenta[b]indoles with high regio- and stereoselectivities. Meanwhile, the iridium-pi-allyl species was recognized as an aza-1,3-dipole in asymmetric [3+2] cycloaddition with in situ generated C1 ammonium enolates, affording pyrrolo[1,2-a]indoles with high diastereo- and enantioselectivities. In addition, the dipolar cycloadditions could be easily scaled-up and several synthetic transformations of the cycloadducts were demonstrated for the rapid synthesis of diverse chiral polycyclic indoles.