Enantioselective Catalytic Allylation of Acyclic Ketiminoesters: Synthesis of α-Fully-Substituted Amino Esters

We report the first direct catalytic enantioselective allylation of acyclic α-ketiminoesters to afford α-allyl-α-aryl and α-allyl-α-trifluoromethyl amino esters in excellent isolated yield (91–99%) and with high optical purity (90–99+% ee). The allylation proceeds on a gram scale with 5–10 mol % of indium(I) iodide and commercially available BOX-type ligands. The allylated products are easily converted to enantiomerically enriched α-substituted proline derivatives.