Useful empirical insights onto the enantioinduction process of chiral Rh(II)carboxylate catalysts are described in the first catalytic asymmetric cyclopropanation of alkenes with alpha-nitro diazoacetophenones. X-ray, solution NMR, and reactivity studies made on these complexes suggest that the level of asymmetric induction strongly depends on their active symmetry, which in turn relies on the nature of the chiral ligands' substituents. The catalyst's 'All Up' reactive conformation resulted in being necessary to obtain good stereoselectivity, and the resulting products are shown to be key intermediates in a concise synthesis of highly enantioenriched cis-cyclopropane alpha-amino acids.