Access to Chiral HWE Reagents by Rhodium-Catalyzed Asymmetric Arylation of γ,δ-Unsaturated β-Ketophosphonates.

Asymmetric arylation of γ,δ-unsaturated β-ketophosphonates with arylboronic acids is reported. By using the ( R)-diene* ligated rhodium(I) chloride complex as a catalyst under none basic conditions, the corresponding β-ketophosphonates bearing a δ-chiral center were obtained in high yields (up to 99%) with good to excellent enantioselectivities (up to >99% ee). The enantioenriched products can be readily converted to diverse chiral β'-aryl enones by the Horner-Wadsworth-Emmons reaction.