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 

机构地区：[1]College of Chemistry and Molecular Sciences,Wuhan University,Wuhan 430072,China [2]State Key Laboratory of Organometallic Chemistry,Shanghai Institute of Organic Chemistry,Shanghai 230021,China [3]Shenzhen Grubbs Institute,Department of Chemistry and Guangdong Provincial Key Laboratory of Catalysis,Southern University of Science and Technology,Shenzhen 518055,China [4]College of Science,Huazhong Agricultural University,Wuhan 430070,China

出　　处：《Science China Chemistry》2023年第11期3193-3204,共12页中国科学（化学英文版）

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)。

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 precursors.Systematic 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.

关 键 词：asymmetric catalysis 1 3-dipolar cycloaddition chiral pyrrolidines HETEROARENE trifluoromethyl group 

分 类 号：O621.251[理学—有机化学]