title: An Enantioselective Bidentate Auxiliary Directed Palladium-Catalyzed Benzylic C-H Arylation of Amines Using a BINOL Phosphate Ligand.
abstract: A new enantioselective palladium(II)-catalyzed benzylic C-H arylation reaction of amines is enabled by the bidentate picolinamide (PA) directing group. This reaction provides the first example of enantioselective benzylic γ-C-H arylations of alkyl amines, and proceeds with up to 97 % ee. The 2,2'-dihydroxy-1,1'-binaphthyl (BINOL) phosphoric acid ligand, Cs2CO3, and solvent-free conditions are essential for high enantioselectivity. Mechanistic studies suggest that multiple BINOL ligands are involved in the stereodetermining C-H palladation step.
authors.affiliation: State Key Laboratory and Institute of Elemento-Organic Chemistry, Collaborative Innovation, Center of Chemical Science and Engineering (Tianjin), Nankai University, Tianjin, 300071, China.
authors.forename: Hao
authors.identifier: 0000-0002-3831-2988
authors.initials: H
authors.lastname: Wang
authors.affiliation: State Key Laboratory and Institute of Elemento-Organic Chemistry, Collaborative Innovation, Center of Chemical Science and Engineering (Tianjin), Nankai University, Tianjin, 300071, China.
authors.forename: Hua-Rong
authors.identifier: 0000-0001-7247-9354
authors.initials: HR
authors.lastname: Tong
authors.affiliation: State Key Laboratory and Institute of Elemento-Organic Chemistry, Collaborative Innovation, Center of Chemical Science and Engineering (Tianjin), Nankai University, Tianjin, 300071, China.
authors.forename: Gang
authors.identifier: 0000-0002-9064-3418
authors.initials: G
authors.lastname: He
authors.affiliation: State Key Laboratory and Institute of Elemento-Organic Chemistry, Collaborative Innovation, Center of Chemical Science and Engineering (Tianjin), Nankai University, Tianjin, 300071, China.|Department of Chemistry, The Pennsylvania State University, University Park, Pennsylvania, 16802, USA.
authors.forename: Gong
authors.identifier: 0000-0002-5067-9889
authors.initials: G
authors.lastname: Chen
keywords: C−H activation; arylations; enantioselectivity; palladium; reaction mechanism