Browsing by Subject "Halogens"

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    Kinetically-controlled ni-catalyzed direct carboxylation of unactivated secondary alkyl bromides without chain walking
    (American Chemical Society, 2024-01-09) 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; Química Inorgánica
    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.