title: Diastereo- and enantioselective iridium-catalyzed allylation of cyclic ketone enolates: synergetic effect of ligands and barium enolates.
abstract: 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.
authors.affiliation: Department of Chemistry, University of California , Berkeley, California 94720, United States.
authors.forename: Wenyong
authors.initials: W
authors.lastname: Chen
authors.forename: Ming
authors.initials: M
authors.lastname: Chen
authors.forename: John F
authors.initials: JF
authors.lastname: Hartwig
mesh_terms: D000475:Alkenes / Q000737:chemistry*; D001464:Barium / Q000737:chemistry*; D002264:Carboxylic Acids / Q000737:chemistry; D007495:Iridium / Q000737:chemistry*; D007659:Ketones / Q000737:chemistry*; D008024:Ligands; D013237:Stereoisomerism
chemical_list: D000475:Alkenes; D002264:Carboxylic Acids; D007659:Ketones; D008024:Ligands; D001464:Barium; D007495:Iridium