The selective activation of inert C-F bonds is one of the most challenging topics in modern organic chemistry. Trifluoromethylketones represent a class of versatile building blocks that are inexpensive and readily available polyfluorinated starting materials. The functionalization of C-F bond in trifluoromethylketones has recently been achieved using difluoroenolates, difluorinated acyl anions or radicals for the synthesis of difluoromethylene compounds. This strategy has also been successfully applied to their derivatives, such as trifluoromethylated esters, amides, diazo compounds and -sulfonylhydrazones, which would be of significant value for the synthesis of partially fluorinated intermediates. In this review, we mainly focus on the recent advances, challenges and perspectives of trifluoromethylated carbonyl compounds and their derivatives C-F bond activation, along with mechanistic insight.
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http://dx.doi.org/10.1039/d2ob00795a | DOI Listing |
J Hazard Mater
December 2024
School of Environmental Science and Engineering, Southern University of Science and Technology, Shenzhen 518055, PR China; Guangdong Provincial Key Laboratory of Soil and Groundwater Pollution Control, Southern University of Science and Technology, Shenzhen 518055, PR China. Electronic address:
The persistence and ecological impact of per- and poly-fluoroalkyl substances (PFAS) in water sources necessitate effective and energy-efficient treatment solutions. This study introduces a novel approach using cerium dioxide (CeO) electrodes enhanced with oxygen vacancy (O) to catalyze the defluorination of PFAS. By leveraging the unique affinity between cerium and fluorine-containing species, our approach enables adsorptive preconcentration and catalytic degradation at low oxidation potentials (1.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Laboratoire de Chimie Supramoléculaire, Institut de Science et d'Ingénierie Supramoléculaires (ISIS), Université de Strasbourg, Strasbourg 67000, France.
SAr reactions were remarkably accelerated using a pretargeting and activating unit based on dynamic covalent chemistry (DCvC). A Cys attack at the C-F bond on the aromatic ring of salicylaldehyde derivatives was only observed upon iminium formation with a neighboring Lys residue of model small peptides. Such self-activation was ascribed to the stronger electron-withdrawing capability of the iminium bond with respect to that of the parent aldehyde that stabilized the transition state of the reaction, together with the higher preorganization of the reactive groups in the cationic aldiminium species.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Hokkaido University: Hokkaido Daigaku, WPI-ICReDD, Kita 21 Nishi 10, Kita-ku, 001-0021, Sapporo, JAPAN.
Fluorine-containing compounds have shown unparalleled impacts in the realm of functional molecules, and the ability to prepare novel structures has been crucial in unlocking new properties for applications in pharmaceutical and materials science. Herein, we report a copper-catalyzed, photoinduced defluorinative C‒O coupling between trifluoromethylarenes and alcohols. This method allows for direct access to a wide selection of difluorobenzylether (ArCF2OR) molecules, including a compound displaying liquid crystal behavior.
View Article and Find Full Text PDFChemistry
December 2024
Huaibei Normal University, Key laboratory of green and precise synthetic chemistry and applications, ministry of education, No.100 Dongshan Road, Xiangshan District, 235000, Huaibei, CHINA.
In this study, we reported a new approach to activate the C-F bond of trifluoromethylarenes to achieve the hydro-difluoroalkylation of arylethylenes using photoexcited Hantzsch esters (HEs) anions. A wide range of α,α-difluoroalkanes was synthesized. Late-stage functionalization of drug molecules and synthesis of bioactive molecule bioisostere were also presented.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2024
Pfizer Inc, Medicinal Chemistry, UNITED STATES OF AMERICA.
The heme paradigm where Fe=O acts as the C-H oxidant and Fe-OH rebounds with the formed carbon-centered radical guides the design of the prototypical synthetic hydroxylation catalyst. We are exploring methods to evolve beyond the metal-oxo oxidant and hydroxide rebound, to incorporate a wider array of functional group. We have demonstrated the application of CoII(OTf)2 (10 mol% catalyst; OTf = trimfluoromethanesulfonate) in combination with polydentate N-donor ligands (e.
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