Asymmetric metal-catalyzed C-H functionalization is a powerful strategy for the rapid generation of complex target molecules from simple precursors. While aryl (pseudo) halides have been used as electrophilic substrates in enantioselective Pd(0)-catalyzed syntheses of N-heterocycles, alternative partners for C-H functionalizations remain underexplored. Herein we describe the first application of ketene aminal phosphates as competent electrophiles in a Pd(0)-catalyzed desymmetrization. This transformation allowed the efficient synthesis of chiral isoindolines in a highly enantioselective fashion. Furthermore, intending to introduce sought-after perfluoroalkyl substituents, we explored intramolecular C-H functionalization of imidoyl chlorides resulting in the asymmetric preparation of previously inaccessible 1H-isoindoles. Tailored chiral monodentate ligands afforded high levels of enantioinduction in both transformations.