Reductive Ti-crossed Claisen condensation between methyl α-bromocarboxylates and acid chlorides utilizing a TiCl 4–PPh 3–N-methylimidazole reagent proceeded smoothly to give the α-monosubstituted and thermodynamically unfavorable α, α-disubstituted β-keto methyl esters in good to excellent yields (33 examples; 73–96% yield).
