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An Enantioselective Bidentate Auxiliary Directed Palladium‐Catalyzed Benzylic C−H Arylation of Amines Using a BINOL Phosphate Ligand
Author(s) -
Wang Hao,
Tong HuaRong,
He Gang,
Chen Gong
Publication year - 2016
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201609337
Subject(s) - enantioselective synthesis , chemistry , palladium , ligand (biochemistry) , denticity , phosphoric acid , catalysis , medicinal chemistry , alkyl , solvent , combinatorial chemistry , stereochemistry , organic chemistry , receptor , crystal structure , biochemistry
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, Cs 2 CO 3 , 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.