An enantioselective cyclopropanation reaction of N-substituted 2-pyridones with diazo compounds has been realized by using a chiral rhodium complex as the catalyst, and the corresponding chiral cyclopropanes could be formed in good yields with high enantioselectivities. Moreover, using acceptor-acceptor dimethyl 2-diazomalonate as the carbene precursor, a novel 1,4-rearrangement of a Boc group from N to C has also been discovered under rhodium catalysis.