A novel divergent tandem one-pot method for the synthesis of 3, 5, 6-trisubstituted 1 H- pyrimidin-2, 4-dione derivatives is developed. In the presence of 10 mol% of Cu (OAc) 2, the α-substituted Blaise reaction intermediates (R2≠ H) reacted with isocyanates chemoselectively to afford pyrimidin-2, 4-diones, whereas the α-unsubstituted Blaise reaction intermediate (R2= H) showed a propensity to be a C-nucleophile toward ...