A tunable procedure on palladium-catalyzed carbonylative divergent synthesis of alpha,beta-unsaturated amides and maleimides from symmetrical internal alkynes and nitroarenes has been developed. By using Pd(acac)(2)/dppp/4-CIBSA/DMF and Pd(TFA)(2)/DPEphos/PTSA/H2O/toluene as the catalytic systems, a range of multi-substituted maleimides and alpha,beta-unsaturated amides were selectively prepared in moderate to good yields with Mo(CO)(6) as the solid CO source and nitroarene as a cheap and abundant nitrogen source. (C) 2019 Elsevier Inc. All rights reserved.