A new strategy for the preparation of highly-substituted dihydroquinoxaline-2(1 H )-ones is reported. The strategy harnesses a divergent NaI-catalyzed amine substitution of mesylates to prepare a range of sterically hindered amidoamine substrates. These substrates are then subjected to Pd(dba) 2 /P( t Bu) 3 mediated cyclization. The preparation of amidoalcohol substrates occurs with reasonable yields (40–84%), with lower yields being obtained with aromatic and bulky amines. Palladium-catalyzed intramolecular C–N bond formation is slow, requiring 10 mol % catalyst loadings for complete conversion in 16 h. All substrates cyclized with reasonable yields (48–73%).
