Diastereo- and enantioselective iridium-catalyzed allylation of cyclic ketone enolates: synergetic effect of ligands and barium enolates.
Published Web Locationhttps://doi.org/10.1021/ja506500u
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.