Chiral Imidazoline–Phosphine Ligands for Palladium-Catalyzed Asymmetric Allylic Substitutions

Chiral imidazoline–phosphine ligands with a 1,1′-binaphthalene framework have been developed as new types of N,P ligands. The chiral ligand <b>L1</b> prepared from (<i>R</i>)-(−)-2-(diphenylphosphino)-1,1′-binaphthyl-2′-acid efficiently affects the palladium-catalyzed enantioselective allylic alkylation of 1,3-diarylpropenyl acetate with dimethyl malonate to give the corresponding adducts in excellent yields and enantioselectivities (up to 96% ee), and chiral ligand <b>L9</b> can be used for the palladium-catalyzed asymmetric allylic monofluoromethylation of 1,3-diphenylpropenyl acetate with 1-fluorobis­(phenylsulfonyl)­methane to afford the corresponding product in excellent enantioselectivities (up to 98% ee) and moderate yields under mild conditions. The bidentate N,P-coordination pattern to the Pd atom with ligand <b>L1</b> has been unambiguously confirmed by X-ray diffraction