Publication: Kinetically-controlled ni-catalyzed direct carboxylation of unactivated secondary alkyl bromides without chain walking
Authors
Davies, Jacob ; Lyonnet, Julien R. ; Carvalho, Bjorn ; Sahoo, Basudev ; Day, Craig S. ; Juliá Hernández, Francisco ; Duan, Yaya ; Obst, Marc ; Norrby, Per-Ola ; Velasco-Rubio, Álvaro ; Hopmann, Kathrin H ; Martin, Ruben ; Obst, Marc ; Per-OLa, Norrby
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Publisher
American Chemical Society
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DOI
https://doi.org/10.1021/jacs.3c11205
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info:eu-repo/semantics/article
Description
© 2024 The Authors. This manuscript version is made available under the CC-BY-NC-ND 4.0 license http://creativecommons.org/licenses/by-nc-nd/4.0/. This document is the Published version of a Published Work that appeared in final form in Journal of the American Chemical Society. To access the final edited and published work see https://doi.org/10.1021/jacs.3c11205
Abstract
Herein, we report the direct carboxylation of unactivated secondary alkyl bromides enabled by the merger of photoredox and nickel catalysis, a previously inaccessible endeavor in the carboxylation arena. Site-selectivity is dictated by a kinetically controlled insertion of CO2 at the initial C(sp3
)−Br site by the rapid formation of Ni(I)−alkyl species, thus avoiding
undesired β-hydride elimination and chain-walking processes. Preliminary mechanistic experiments reveal the subtleties of stereoelectronic effects for guiding the reactivity and site-selectivity.
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Citation
J. Am. Chem. Soc. 2024, 146, 3, 1753–1759
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