title: Stereodivergent Allylic Substitutions with Aryl Acetic Acid Esters by Synergistic Iridium and Lewis Base Catalysis.
abstract: The preparation of all possible stereoisomers of a given chiral molecule bearing multiple stereocenters by a simple and unified method is a significant challenge in asymmetric catalysis. We report stereodivergent allylic substitutions with aryl acetic acid esters catalyzed synergistically by a metallacyclic iridium complex and benzotetramisole. Through permutations of the enantiomers of the two chiral catalysts, all four stereoisomers of the products bearing two adjacent stereocenters are accessible with high diastereoselectivity and enantioselectivity. The resulting chiral activated ester products can be converted readily to enantioenriched amides, unactivated esters, and carboxylic acids in a one-pot manner.
authors.affiliation: Department of Chemistry, University of California , Berkeley, California 94720, United States.
authors.forename: Xingyu
authors.initials: X
authors.lastname: Jiang
authors.affiliation: Department of Chemistry, University of California , Berkeley, California 94720, United States.
authors.forename: Jason J
authors.initials: JJ
authors.lastname: Beiger
authors.affiliation: Department of Chemistry, University of California , Berkeley, California 94720, United States.
authors.forename: John F
authors.identifier: 0000-0002-4157-468X
authors.initials: JF
authors.lastname: Hartwig
mesh_terms: D000085:Acetates / Q000737:chemistry*; D000498:Allyl Compounds / Q000737:chemistry*; D000577:Amides / Q000138:chemical synthesis / Q000737:chemistry; D002264:Carboxylic Acids / Q000138:chemical synthesis / Q000737:chemistry; D002384:Catalysis; D004952:Esters / Q000138:chemical synthesis / Q000737:chemistry*; D007495:Iridium / Q000737:chemistry*; D058115:Lewis Bases / Q000737:chemistry*; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D000085:Acetates; D000498:Allyl Compounds; D000577:Amides; D002264:Carboxylic Acids; D004952:Esters; D058115:Lewis Bases; D009942:Organometallic Compounds; D007495:Iridium