709-21-7Relevant articles and documents
Circumventing Intrinsic Metal Reactivity: Radical Generation with Redox-Active Ligands
Jacquet, Jérémy,Cheaib, Khaled,Ren, Yufeng,Vezin, Hervé,Orio, Maylis,Blanchard, Sébastien,Fensterbank, Louis,Desage-El Murr, Marine
, p. 15030 - 15034 (2017)
Nickel complexes have gained sustained attention as efficient catalysts in cross-coupling reactions and co-catalysts in dual systems due to their ability to react with radical species. Central to this reactivity is nickel's propensity to shuttle through several accessible redox states from Ni0 to NiIV. Here, we report the catalytic generation of trifluoromethyl radicals from a nickel complex bearing redox-active iminosemiquinone ligands. This unprecedented reactivity is enabled through ligand-based oxidation performing electron transfer to an electrophilic CF3+ source while the nickel oxidation state is preserved. Additionally, extension of this reactivity to a copper complex bearing a single redox equivalent is reported, thus providing a unified reactivity scheme. These results open new pathways in radical chemistry with redox-active ligands.
Rhodium-catalyzed α-fluoroalkylation reaction of ketones using silyl enol ethers
Sato, Kazuyuki,Higashinagata, Makoto,Yuki, Takashi,Tarui, Atsushi,Omote, Masaaki,Kumadaki, Itsumaro,Ando, Akira
, p. 51 - 55 (2008)
The treatment of silyl enol ethers with fluoroalkyl halides (Rf-X) in the presence of RhCl(PPh3)3 gave α-fluoroalkylated ketones. It seems that a rhodium complex derived from the silyl enol ether and RhCl(PPh3)
A General Organocatalytic System for Electron Donor-Acceptor Complex Photoactivation and Its Use in Radical Processes
De Pedro Beato, Eduardo,Melchiorre, Paolo,Spinnato, Davide,Zhou, Wei
supporting information, p. 12304 - 12314 (2021/08/20)
We report herein a modular class of organic catalysts that, acting as donors, can readily form photoactive electron donor-acceptor (EDA) complexes with a variety of radical precursors. Excitation with visible light generates open-shell intermediates under mild conditions, including nonstabilized carbon radicals and nitrogen-centered radicals. The modular nature of the commercially available xanthogenate and dithiocarbamate anion organocatalysts offers a versatile EDA complex catalytic platform for developing mechanistically distinct radical reactions, encompassing redox-neutral and net-reductive processes. Mechanistic investigations, by means of quantum yield determination, established that a closed catalytic cycle is operational for all of the developed radical processes, highlighting the ability of the organic catalysts to turn over and iteratively drive every catalytic cycle. We also demonstrate how the catalysts' stability and the method's high functional group tolerance could be advantageous for the direct radical functionalization of abundant functional groups, including aliphatic carboxylic acids and amines, and for applications in the late-stage elaboration of biorelevant compounds and enantioselective radical catalysis.
Electrochemical Synthesis of Fluorinated Ketones from Enol Acetates and Sodium Perfluoroalkyl Sulfinates
Vil’, Vera A.,Merkulova, Valentina M.,Ilovaisky, Alexey I.,Paveliev, Stanislav A.,Nikishin, Gennady I.,Terent’ev, Alexander O.
supporting information, p. 5107 - 5112 (2021/06/30)
The electrochemical synthesis of fluorinated ketones from enol acetates and RfSO2Na in an undivided cell under constant current conditions was developed. The electrosynthesis proceeded via perfluoroalkyl radical generation from sodium perfluoroalkyl sulfinate followed by addition to the enol acetate and transformation of the resulting C radical to a fluorinated ketone. The method is applicable to a wide range of enol acetates and results in the desired products in yields of 20 to 85%.
