title: Iridium-Catalyzed Diastereoselective and Enantioselective Allylic Substitutions with Acyclic α-Alkoxy Ketones.
abstract: The asymmetric alkylation of acyclic ketones is a longstanding challenge in organic synthesis. Reported herein are diastereoselective and enantioselective allylic substitutions with acyclic α-alkoxy ketones catalyzed by a metallacyclic iridium complex to form products with contiguous stereogenic centers derived from the nucleophile and electrophile. These reactions occur between allyl methyl carbonates and unstabilized copper(I) enolates generated in situ from acyclic α-alkoxy ketones. The resulting products can be readily converted into enantioenriched tertiary alcohols and tetrahydrofuran derivatives without erosion of enantiomeric purity.
authors.affiliation: Department of Chemistry, University of California, Berkeley, CA, 94720, USA.|Division of Chemical Sciences, Lawrence Berkeley National Laboratory, Berkeley, CA, 94720, USA.
authors.forename: Xingyu
authors.identifier: 0000-0002-4170-3736
authors.initials: X
authors.lastname: Jiang
authors.affiliation: Department of Chemistry, University of California, Berkeley, CA, 94720, USA.|Division of Chemical Sciences, Lawrence Berkeley National Laboratory, Berkeley, CA, 94720, USA.
authors.forename: Wenyong
authors.initials: W
authors.lastname: Chen
authors.affiliation: Department of Chemistry, University of California, Berkeley, CA, 94720, USA. jhartwig@berkeley.edu.|Division of Chemical Sciences, Lawrence Berkeley National Laboratory, Berkeley, CA, 94720, USA. jhartwig@berkeley.edu.
authors.forename: John F
authors.initials: JF
authors.lastname: Hartwig
mesh_terms: D000498:Allyl Compounds / Q000737:chemistry*; D002384:Catalysis; D056831:Coordination Complexes / Q000737:chemistry; D003300:Copper / Q000737:chemistry; D007495:Iridium / Q000737:chemistry*; D007659:Ketones / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D000498:Allyl Compounds; D056831:Coordination Complexes; D007659:Ketones; D007495:Iridium; D003300:Copper
keywords: alkylation; asymmetric catalysis; diastereoselectivity; iridium; ketones