Asymmetric α-Allylation of α-Substituted β-Ketoesters with Allyl Alcohols.

Enantioselective α-allylation of α-substituted β-ketoesters with simple allyl alcohols was successfully performed by synergistic catalysis with the catalyst combination of a chiral primary amino acid and an achiral palladium complex without additional promotors like acids or bases. The allylation reaction and generation of a chiral quaternary carbon stereocenter proceeded smoothly to produce α,α-disubstituted β-ketoesters in high yields (91-99%) with high enantioselectivities (90-99% ee).