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A novel class of chiral naphthyridine diimine ligands (NDI*) readily accessible from C2‐symmetric 2,6‐di‐(1‐arylethyl)anilines is described. The utility of these ligands, particularly one with fluorinated aryl side arms, is demonstrated by a reductive Ni‐catalyzed enantioselective alkylidene transfer reaction from 1,1‐dichloroalkenes to olefins. This transformation provides direct access to a broad range of synthetically valuable alkylidenecyclopropanes in high yields and enantioselectivities.