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

作　　者：Fei Tian Wu-Lin Yang Tao Ni Jian Zhang Wei-Ping Deng 

机构地区：[1]Shanghai Key Laboratory of New Drug Design and School of Pharmacy,East China University of Science and Technology,Shanghai 200237,China

出　　处：《Science China Chemistry》2021年第1期34-40,共7页中国科学（化学英文版）

基　　金：the National Natural Science Foundation of China(21901072);the China Postdoctoral Science Foundation(2019T120310);Shanghai Sailing Program(18YF140560)。

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-π-allyl species tended to serve as an all-carbon 1,3-dipole in the asymmetric[3+2]cycloaddition with electrondeficient alkenes,which furnished polysubstituted cyclopenta[b]indoles with high regio-and stereoselectivities.Meanwhile,the iridium-π-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-α]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.

关 键 词：palladium catalysis iridium catalysis asymmetric synthesis dipolar cycloaddition polycyclic indoles 

分 类 号：O626.13[理学—有机化学]