Chiral cyclopentadienyl Rh-III complexes efficiently catalyze enantioselective cyclopropanations of electron-deficient olefins with N- enoxysuccinimides as the C1 unit. Excellent asymmetric inductions and high diastereoselectivities can be obtained for a wide range of substrate combinations. The reaction proceeds under mild conditions without precautions to exclude air and water. Moreover, the synthetic utility of the developed method is demonstrated by concise syntheses of members of the oxylipin natural products family and the KMO inhibitor UPF-648.