An Enantioselective Bidentate Auxiliary Directed Palladium‐Catalyzed Benzylic C−H Arylation of Amines Using a BINOL Phosphate Ligand |
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| Authors: | Hao Wang Hua‐Rong Tong Prof?Dr Gang He Prof?Dr Gong Chen |
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| Institution: | 1. State Key Laboratory and Institute of Elemento-Organic Chemistry, Collaborative Innovation, Center of Chemical Science and Engineering (Tianjin), Nankai University, Tianjin, China;2. Department of Chemistry, The Pennsylvania State University, Pennsylvania, USA |
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| 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. |
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| Keywords: | arylations C− H activation enantioselectivity palladium reaction mechanism |
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