5653-09-8Relevant articles and documents
Nickel-Catalyzed Reductive Acylation of Carboxylic Acids with Alkyl Halides and N-Hydroxyphthalimide Esters Enabled by Electrochemical Process
Zhou, Xiao,Guo, Lin,Zhang, Haoxiang,Xia, Raymond Yang,Yang, Chao,Xia, Wujiong
, p. 1526 - 1531 (2022/03/31)
A sustainable Ni-catalyzed reductive acylation reaction of carboxylic acids via an electrochemical pathway is presented, affording a variety of ketones as major products. The reaction proceeds at ambient temperature using unactivated alkyl halides and N-hydroxyphthalimide (NHP) esters as coupling partners, which exhibits several synthetic advantages, including mild conditions and convenience of amplification (58% yield for 6 mmol scale reaction). (Figure presented.).
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.
Stereodivergent Alkyne Hydrofluorination Using Protic Tetrafluoroborates as Tunable Reagents
Geaneotes, Paul,Guo, Rui,Liu, Peng,Qi, Xiaotian,Wang, Ruihan,Wang, Yi-Ming,Xiang, Hengye
supporting information, p. 16651 - 16660 (2020/07/16)
The discovery of safe, general, and practical procedures to prepare vinyl fluorides from readily available precursors remains a synthetic challenge. The metal-free hydrofluorination of alkynes constitutes an attractive though elusive strategy for their preparation. Introduced here is an inexpensive and easily handled reagent that enables the development of simple and scalable protocols for the regioselective hydrofluorination of alkynes to access both the E and Z isomers of vinyl fluorides. These reaction conditions were suitable for a diverse collection of alkynes, including several highly functionalized pharmaceutical derivatives. Computational and experimental mechanistic studies support C?F bond formation through vinyl cation intermediates, with the E- and Z-hydrofluorination products forming under kinetic and thermodynamic control, respectively.
