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 Robert Li-Yuan Bao;Lei Shi;Kang Fu

作者机构：School of ScienceHarbin Institute of TechnologyShenzhen 518055China State Key Laboratory of Elemento-Organic ChemistryNankai UniversityTianjin 300071China Guangdong Provincial Key Laboratory of CatalysisSouthern University of Science and TechnologyShenzhen 518055China School of Chemistry and Chemical EngineeringHarbin Institute of TechnologyHarbin 150001China 

出 版 物：《Chinese Chemical Letters》 (中国化学快报（英文版）)

年 卷 期：2022年第33卷第5期

页      面：2415-2419页

核心收录：

学科分类：07[理学] 070304[理学-物理化学(含∶化学物理)] 070303[理学-有机化学] 0703[理学-化学] 

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)。 

主　　题：Chiral bisoxazoline ligand Chiral pocket Chiral spiro ligand Friedel-Crafts reaction Trifluoromethylated all-carbon quaternary stereocenter 

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.