Diastereo- and Enantioselective Iridium-Catalyzed Allylation of Cyclic Ketone Enolates: Synergetic Effect of Ligands and Barium Enolates

We report asymmetric allylic alkylation of barium enolates of cyclic ketones catalyzed by a metalla­cyclic iridium complex containing a phosphor­amidite ligand derived from (R)-1-(2-naphthyl)­ethylamine. The reaction products contain adjacent quaternary and tertiary stereocenters. This process demonstrates that unstabilized cyclic ketone enolates can undergo diastereo- and enantio­selective Ir-catalyzed allylic substitution reactions with the proper choice of enolate counter­cation. The products of these reactions can be conveniently transformed to various useful poly­carbo­cyclic structures.