title: Mechanistic studies of copper(I)-catalyzed 1,3-halogen migration.
abstract: An ongoing challenge in modern catalysis is to identify and understand new modes of reactivity promoted by earth-abundant and inexpensive first-row transition metals. Herein, we report a mechanistic study of an unusual copper(I)-catalyzed 1,3-migration of 2-bromostyrenes that reincorporates the bromine activating group into the final product with concomitant borylation of the aryl halide bond. A combination of experimental and computational studies indicated this reaction does not involve any oxidation state changes at copper; rather, migration occurs through a series of formal sigmatropic shifts. Insight provided from these studies will be used to expand the utility of aryl copper species in synthesis and develop new ligands for enantioselective copper-catalyzed halogenation.
authors.affiliation: †Department of Chemistry, University of Wisconsin, Madison, Wisconsin 53706, United States.
authors.forename: Ryan
authors.initials: R
authors.lastname: Van Hoveln
authors.affiliation: ‡Department of Chemistry, University of California, Davis, California 95616, United States.
authors.forename: Brandi M
authors.initials: BM
authors.lastname: Hudson
authors.affiliation: ‡Department of Chemistry, University of California, Davis, California 95616, United States.
authors.forename: Henry B
authors.initials: HB
authors.lastname: Wedler
authors.affiliation: †Department of Chemistry, University of Wisconsin, Madison, Wisconsin 53706, United States.
authors.forename: Desiree M
authors.initials: DM
authors.lastname: Bates
authors.affiliation: †Department of Chemistry, University of Wisconsin, Madison, Wisconsin 53706, United States.
authors.forename: Gabriel
authors.initials: G
authors.lastname: Le Gros
authors.affiliation: ‡Department of Chemistry, University of California, Davis, California 95616, United States.
authors.forename: Dean J
authors.initials: DJ
authors.lastname: Tantillo
authors.affiliation: †Department of Chemistry, University of Wisconsin, Madison, Wisconsin 53706, United States.
authors.forename: Jennifer M
authors.initials: JM
authors.lastname: Schomaker
mesh_terms: D001966:Bromine / Q000737:chemistry*; D002384:Catalysis; D003300:Copper / Q000737:chemistry*; D054879:Halogenation; D008958:Models, Molecular; D010084:Oxidation-Reduction; D013343:Styrenes / Q000737:chemistry*
chemical_list: D013343:Styrenes; D003300:Copper; D001966:Bromine; C519197:4-bromostyrene
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