A copper-based catalytic system has been developed to enable formal [3 + 1 + 2] annulations of ketoxime acetates, aldehydes, and cyanamides. This protocol offers a new strategy for the synthesis of highly substituted 2-aminopyrimidine compounds, and more importantly, pyrimidines have now been included in the N-heterocycle family constructed using O-acyl ketoximes as N-C-C synthons.