A highly efficient catalytic asymmetric α-addition of isocyanides to alkylidene malonates was accomplished. The process was based on the utilization of a chiral N,N'-dioxide/MgII catalyst, delivering a variety of 2-alkyl-5-aminooxazoles in up to 99% yield and 96% ee under mild reaction conditions. Besides, a chiral imide and dipeptide could be easily obtained by ring-opening of the oxazole product, both of which are important structural motifs for many biologically active compounds. Based on the experimental investigations and previous work, a possible transition state model was proposed.