Login / Signup

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

Jacob DaviesJulien R LyonnetBjørn CarvalhoBasudev SahooCraig S DayFrancisco Juliá-HernándezYaya Duannull Álvaro Velasco-RubioMarc ObstPer-Ola NorrbyKathrin Helen HopmannRúben Martín
Published in: Journal of the American Chemical Society (2024)
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.
Keyphrases
  • visible light
  • ionic liquid
  • metal organic framework
  • room temperature
  • lower limb
  • single cell
  • structural basis
  • reduced graphene oxide
  • sensitive detection