Mechanistic Studies of Copper(I)-Catalyzed 1,3-Halogen Migration

Ryan Van Hoveln, Brandi M Hudson, Henry B Wedler, Desiree M Bates, Gabriel Le Gros, Dean J Tantillo, Jennifer M Schomaker: Mechanistic Studies of Copper(I)-Catalyzed 1,3-Halogen Migration. In: Journal of the American Chemical Society, 137 (16), pp. 5346-5354, 2015, ISSN: 0002-7863.

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.

BibTeX (Download)

@article{VanHoveln2015,
title = {Mechanistic Studies of Copper(I)-Catalyzed 1,3-Halogen Migration},
author = {Ryan Van Hoveln and Brandi M Hudson and Henry B Wedler and Desiree M Bates and Gabriel Le Gros and Dean J Tantillo and Jennifer M Schomaker},
url = {https://doi.org/10.1021/ja511236d},
doi = {10.1021/ja511236d},
issn = {0002-7863},
year  = {2015},
date = {2015-04-29},
journal = {Journal of the American Chemical Society},
volume = {137},
number = {16},
pages = {5346-5354},
publisher = {American Chemical Society},
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.},
keywords = {catalysts, copper, genetics, ligands, pharmaceuticals},
pubstate = {published},
tppubtype = {article}
}

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