N-Acylimines are important intermediates in organic synthesis, which have electron-withdrawing acyl substituents to overcome the low electrophilicity and limited utility of N-alkylamines and N-arylamines. They have been utilized in numerous C-C and C-heteroatom bond forming reactions. However, N-acylimines are known to be too unstable to be stored and easily tautomerized to corresponding enamide. Thus, they are generally prepared in situ for the reaction with nucleophiles. We synthesized various N-acylketimines including enolizable aliphatic ones from the alkyl azides in a one-pot procedure. And we demonstrated the utility of cyclic N-acyl ketimine in nucleophilic addition of Grignard reagent to afford acetamide with high diastereoselectivity.