Kinetically-Controlled Ni-Catalyzed Direct Carboxylation of Unactivated Secondary Alkyl Bromides without Chain Walking.

Autor: Davies J; Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology, 43007 Tarragona, Spain., Lyonnet JR; Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology, 43007 Tarragona, Spain.; Universitat Rovira i Virgili, Departament de Química Orgànica, 43007 Tarragona, Spain., Carvalho B; Department of Chemistry, UiT The Arctic University of Norway, N-9307 Tromsø, Norway., Sahoo B; Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology, 43007 Tarragona, Spain., Day CS; Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology, 43007 Tarragona, Spain.; Universitat Rovira i Virgili, Departament de Química Orgànica, 43007 Tarragona, Spain., Juliá-Hernández F; Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology, 43007 Tarragona, Spain., Duan Y; Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology, 43007 Tarragona, Spain., Álvaro Velasco-Rubio; Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology, 43007 Tarragona, Spain., Obst M; Department of Chemistry, UiT The Arctic University of Norway, N-9307 Tromsø, Norway., Norrby PO; Data Science & Modelling, Pharmaceutical Sciences, R&D, AstraZeneca Gothenburg, SE-431 83 Mölndal, Sweden., Hopmann KH; Department of Chemistry, UiT The Arctic University of Norway, N-9307 Tromsø, Norway., Martin R; Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology, 43007 Tarragona, Spain.; ICREA, 08010 Barcelona, Spain.
Jazyk: angličtina
Zdroj: Journal of the American Chemical Society [J Am Chem Soc] 2024 Jan 24; Vol. 146 (3), pp. 1753-1759. Date of Electronic Publication: 2024 Jan 09.
DOI: 10.1021/jacs.3c11205
Abstrakt: 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 CO 2 at the initial C(sp 3 )-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.
Databáze: MEDLINE