SPANphos Ligands in Palladium-Catalyzed Asymmetric Fluorination

The synthesis of new enantiopure wide‐bite‐angle diphosphanes is described as well as their use in the palladium‐catalyzed asymmetric fluorination of α‐cyanoacetates. Enantiomeric excesses up to 93 % were obtained when Pd(OAc)2‐SPANphos was used as catalyst for the fluorination of ethyl 2‐cyano‐2‐phenylacetate with N‐fluorobenzenesulfonimide (NFSI). A trans‐coordinating diphosphane in asymmetric fluorination catalysis? New enantiopure wide‐bite‐angle diphosphanes were synthesized and used in the palladium‐catalyzed asymmetric fluorination of α‐cyanoacetates. Enantiomeric excesses up to 93 % were obtained using Pd(OAc)2‐SPANphos as the catalyst for the fluorination of ethyl 2‐cyano‐2‐phenylacetate with N‐fluorobenzenesulfonimide (NFSI).