title: Functional-group-tolerant, nickel-catalyzed cross-coupling reaction for enantioselective construction of tertiary methyl-bearing stereocenters.
abstract: The first Negishi nickel-catalyzed stereospecific cross-coupling reaction of secondary benzylic esters is reported. A series of traceless directing groups is evaluated for ability to promote cross-coupling with dimethylzinc. Esters with a chelating thioether derived from commercially available 2-(methylthio)acetic acid are most effective. The products are formed in high yield and with excellent stereospecificity. A variety of functional groups are tolerated in the reaction including alkenes, alkynes, esters, amines, imides, and O-, S-, and N-heterocycles. The utility of this transformation is highlighted in the enantioselective synthesis of a retinoic acid receptor agonist and a fatty acid amide hydrolase inhibitor.
authors.affiliation: Department of Chemistry, University of California, Irvine, California 92697-2025, USA.
authors.forename: Hanna M
authors.initials: HM
authors.lastname: Wisniewska
authors.forename: Elizabeth C
authors.initials: EC
authors.lastname: Swift
authors.forename: Elizabeth R
authors.initials: ER
authors.lastname: Jarvo
mesh_terms: D001555:Benzene Derivatives / Q000737:chemistry*; D002384:Catalysis; D004952:Esters / Q000737:chemistry; D008745:Methylation; D009532:Nickel / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D001555:Benzene Derivatives; D004952:Esters; D009532:Nickel