Enantioselective anti-Michael hydroarylation of unsaturated carbonyl compounds

While methods to transform α , β -unsaturated carbonyl compounds into compounds bearing β -chiral centers are abundant, enantioselective construction of α -chiral carbonyl compounds from the same starting material remains largely unexplored. Herein, we report a palladium-catalyzed reaction for constructing chiral α -arylated amides and esters through an α -hydroarylation reaction using acrylamides and acrylates as starting materials. Extensive ligand screening revealed the trans -bisphosphine ( S , S )-( R , R )-PhTRAP as a uniquely effective ligand. A wide range of aryl and azaheteroaryl iodides smoothly couple with acrylamides under substantially mild conditions, affording α -arylated amides in high to excellent yields with excellent enantioselectivity. Insights towards the catalytic cycle and the uniqueness of the trans -spanning PhTRAP ligand in controlling regio- and enantioselectivity while suppressing hydrodehalogenation are gained through density functional theory (DFT) studies.