title: Enantioselective formation of cyano-bearing all-carbon quaternary stereocenters: desymmetrization by copper-catalyzed N-arylation.
abstract: The enantioselective construction of all-carbon quaternary stereocenters is one of the most challenging fields in asymmetric synthesis. An asymmetric desymmetrization strategy offers an indirect and efficient method for the formation of all-carbon stereocenters. An enantioselective formation of cyano-bearing all-carbon quaternary stereocenters in 1,2,3,4,-tetrahydroquinolines and 2,3,4,5-tetrahydro-1H-benzo[b]azepines by copper-catalyzed desymmetric N-arylation is demonstrated. The cyano group at the prochiral center plays a key role for the high enantioselectivity and works as an important functional group for further transformations. DFT studies provide a model which successfully accounts for the origin of enantioselectivity.
authors.affiliation: Guangzhou Institutes of Biomedicine and Health, Chinese Academy of Sciences (GIBH), No.190 Kaiyuan Avenue, Guangzhou Science Park, Guangzhou, 510530 (China); Current Address: Molecular Catalyst Research Center, Chubu University, Aichi, 487-8501 (Japan).
authors.forename: Fengtao
authors.initials: F
authors.lastname: Zhou
authors.forename: Gui-Juan
authors.initials: GJ
authors.lastname: Cheng
authors.forename: Wenqiang
authors.initials: W
authors.lastname: Yang
authors.forename: Yan
authors.initials: Y
authors.lastname: Long
authors.forename: Shasha
authors.initials: S
authors.lastname: Zhang
authors.forename: Yun-Dong
authors.initials: YD
authors.lastname: Wu
authors.forename: Xinhao
authors.initials: X
authors.lastname: Zhang
authors.forename: Qian
authors.initials: Q
authors.lastname: Cai
mesh_terms: D001552:Benzazepines / Q000138:chemical synthesis; D002384:Catalysis; D003300:Copper / Q000737:chemistry*; D007546:Isoquinolines / Q000138:chemical synthesis; D008024:Ligands; D008958:Models, Molecular; D008968:Molecular Conformation; D013237:Stereoisomerism
chemical_list: D001552:Benzazepines; D007546:Isoquinolines; D008024:Ligands; D003300:Copper
keywords: asymmetric catalysis; chirality; copper; heterocycles; synthetic methods