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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.

SUBMITTER: Van Hoveln R

PROVIDER: S-EPMC4701576 | biostudies-literature | 2015 Apr

REPOSITORIES: biostudies-literature

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Mechanistic studies of copper(I)-catalyzed 1,3-halogen migration.

Van Hoveln Ryan R Hudson Brandi M BM Wedler Henry B HB Bates Desiree M DM Le Gros Gabriel G Tantillo Dean J DJ Schomaker Jennifer M JM

Journal of the American Chemical Society 20150416 16

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 ox ...[more]

PMID: 25828031

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