Copper-catalyzed asymmetric 1,3-dipolar cycloaddition of azomethine ylides withβ-trifluoromethyl-substituted alkenyl heteroarenes

作     者：Xiang Cheng Xin Chang Yuhong Yang Zongpeng Zhang Jing Li Yipu Li Wenxiao Zhao Lung Wa Chung Huailong Teng Xiu-Qin Dong Chun-Jiang Wang 

作者机构：College of Chemistry and Molecular SciencesWuhan UniversityWuhan 430072China State Key Laboratory of Organometallic ChemistryShanghai Institute of Organic ChemistryShanghai 230021China Shenzhen Grubbs InstituteDepartment of Chemistry and Guangdong Provincial Key Laboratory of CatalysisSouthern University of Science and TechnologyShenzhen 518055China College of ScienceHuazhong Agricultural UniversityWuhan 430070China 

出 版 物：《Science China Chemistry》 (中国科学(化学英文版))

年 卷 期：2023年第66卷第11期

页      面：3193-3204页

核心收录：

学科分类：081704[工学-应用化学] 07[理学] 08[工学] 0817[工学-化学工程与技术] 070303[理学-有机化学] 0703[理学-化学] 

基　　金：supported by the National Natural Science Foundation of China(22071186,22071187,22073067,22101216,22271226,21933003,22193020,22193023) the National Youth Talent Support Program the Natural Science Foundation of Hubei Province(2020CFA0362021CFA069) the Fundamental Research Funds for the Central Universities(2042022kf1180,2042022kf1040) the Shenzhen Nobel Prize Scientists Laboratory Project(C17783101) the Guangdong Provincial Key Laboratory of Catalytic Chemistry(2020B121201002) 

主　　题：asymmetric catalysis 1 3-dipolar cycloaddition chiral pyrrolidines heteroarene trifluoromethyl group 

摘      要：Copper-catalyzed asymmetric 1,3-dipolar cycloaddition of azomethine ylides andβ-trifluoromethyl-substituted alkenyl heteroarenes was developed for the first time.A wide range of enantioenriched pyrrolidines containing both heteroarenes and trifluoromethyl group with multiple stereogenic centers could be readily accessible by this method with good to high yields and excellent levels of both stereo-and regioselectivity(up to 99%yield,20:1 rr,20:1 dr,and up to 95%ee).Notably,substratecontrolled umpolung-type dipolar cycloaddition was also disclosed in this protocol to achieve regiodivergent synthesis withα-aryl substituted aldimine esters as the dipole *** DFT studies were conducted to explore the origin of the stereo-and regioselectivity of this 1,3-dipolar cycloaddition,and suggest that copper(Ⅱ)salt utilized in this catalytic system could be reduced in-situ to the active copper(Ⅰ)species and might be responsible for the observed high stereo-and regioselectivity.