Catalytic Enantioselective Synthesis of Quaternary All-Carbon Stereogenic Centers. Preparation of α,α‘-Disubstituted β,γ-Unsaturated Esters through Cu-Catalyzed Asymmetric Allylic Alkylations

[reaction: see text] Peptide-based chiral ligands, readily prepared from commercially available materials, are used to promote Cu-catalyzed asymmetric allylic alkylations of alpha,beta-unsaturated esters bearing a gamma-phosphate with various alkylzinc reagents. These transformations lead to the formation of alpha,alpha'-dialkyl-beta,gamma-unsaturated esters in high yields as well as high regio- (re) and enantioselectivities (ee).