The Ag-I catalyzed [C+NC+CC] coupling reaction of a 2,3-bisaminoaldehyde 5, L-glycyl sultam 6, and methyl acrylate provides highly functionalized pyrrolidine 7, the key intermediate in an efficient synthetic approach to the cyanocycline and bioxalomycin families of natural products. This powerful multicomponent reaction-based strategy reduces the number of steps needed to make these complex targets by more than one-third and paves the way for biological and biochemical evaluation of this natural product family.