A one-pot protocol toward several substituted nitroolefins 4 and 6 starting with substituted acetones 2 and 5 was described. A facile process was carried out for the triflation of substituted acetones 2 and 5 with triflic anhydride (Tf2O) under the basic condition (Cs2CO3) and then palladium-catalyzed cross-coupling of enol triflates 3 with NaNO2 and BINAP in the presence of phase-transfer reagents (n-Bu4NBr) under the refluxing 1, 2- ...