Highly enantioselective construction of CF_(3) -bearing all-carbon quaternary stereocenters: Chiral spiro-fused bisoxazoline ligands with 1,1'-binaphthyl sidearm for asymmetric Michael-type Friedel-Crafts reaction  

作　　者：Robert Li-Yuan Bao Lei Shi Kang Fu 

机构地区：[1]School of Science,Harbin Institute of Technology,Shenzhen 518055,China [2]State Key Laboratory of Elemento-Organic Chemistry,Nankai University,Tianjin 300071,China [3]Guangdong Provincial Key Laboratory of Catalysis,Southern University of Science and Technology,Shenzhen 518055,China [4]School of Chemistry and Chemical Engineering,Harbin Institute of Technology,Harbin 150001,China

出　　处：《Chinese Chemical Letters》2022年第5期2415-2419,共5页中国化学快报（英文版）

基　　金：support from the National Natural Science Foundation of China(No.21871067);the Natural Science Foundation of Guangdong Province(Nos.2018A030313038 and 2021A1515010190);the Shenzhen Fundamental Research Projects(No.JCYJ20180306171838187);the Harbin Institute of Technology(Shenzhen)(Talent Development Starting Fund from Shenzhen Government);the Open Project Program of State Key Laboratory of Elemento-Organic Chemistry(No.202009);the Guangdong Provincial Key Laboratory of Catalysis(No.2020B121201002)。

摘　　要：A novel class of chiral spiro-fused bisoxazoline ligands possessing a deep chiral pocket was prepared.The developed ligands have been employed in the nickel-catalyzed highly enantioselective Michael-type Friedel-Crafts reaction, affording the products bearing a trifluoromethylated all-carbon quaternary stereocenter with moderate to excellent yields(up to 99%) and good to excellent enantioselectivies(up to> 99.9% ee). Moreover, a proposed model of chiral pocket revealed that the attack of indole from the Re-face of β-CF_(3)-β-disubstituted nitroalkene was favorable.

关 键 词：Chiral bisoxazoline ligand Chiral pocket Chiral spiro ligand Friedel-Crafts reaction Trifluoromethylated all-carbon quaternary stereocenter 

分 类 号：O641.4[理学—物理化学] O621.251[理学—化学]