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).