Reductive Ti-crossed Claisen condensation between methyl alpha-bromocarboxylates and acid chlorides utilizing a TiCl4-PPh3-N-methylimidazole reagent proceeded smoothly to give the alpha-monosubstituted and thermodynamically unfavorable alpha,alpha-disubstituted beta-keto methyl esters in good to excellent yields (33 examples; 73-96% yield).