Remote stereocontrol in the(4+2)cycloadditions of 1,7-zwitterions:Asymmetric synthesis of multifunctionalized tetrahydroquinoline derivatives  

作　　者：Chen Chen Jin Zhou Jing Jiang Yang Li Ting Mao Cheng Peng Gu Zhan Wei Huang 

机构地区：[1]State Key Laboratory of Southwestern Chinese Medicine Resources,School of Pharmacy,Chengdu University of Traditional Chinese Medicine,Chengdu 611137,China

出　　处：《Chinese Chemical Letters》2024年第1期222-226,共5页中国化学快报（英文版）

基　　金：the National Natural Science Foundation of China(Nos.82073997 and 22001024);the Science&Technology Department of Sichuan Province(Nos.2021YFS0044 and 2021YJ0402);Innovation Team and Talents Cultivation Program of National Administration of Traditional Chinese Medicine(No.ZYYCXTD-D-202209);Xinglin Scholar Research Promotion Project of Chengdu University of TCM.

摘　　要：The scope of stereochemistry recognition usually occurs near the chiral scaffold of a ligand or catalyst.Remote stereocontrol,which can surpass the limits of stereorecognition of remote prochiral centers,has long been a challenging object of great interest in asymmetric catalysis.The current work realized the remote stereocontrol of 1,7-zwitterion intermediates formed from Huang's o-amino aryl MBH carbonates.With simple and easily accessibleβ-ICD as the bifunctional catalyst,multifunctionalized tetrahydroquinoline derivatives could be synthesized via(4+2)cycloadditions with excellent enantioselectivity and diastereoselectivity under mild conditions.The strategy possesses broad substrate scope,and three types of electron-deficient enones are successfully applied.Mechanistic studies disclosed the Lewis base-catalyzed reaction pathway,and H-bonding between the catalyst and enones is crucial for long-range stereocontrol.Scale-up reaction and transformations of the tetrahydroquinoline products demonstrated the potential of this strategy.

关 键 词：Asymmetric synthesis TETRAHYDROQUINOLINE Remote stereocontrol PYRAZOLONE Lewis base catalysis 1 7-Zwitterion 

分 类 号：O62[理学—有机化学]