Direct trifluoromethylation of arenes using TFA as the trifluoromethylating reagent was achieved with Ag as the catalyst. This reaction not only provides a new protocol for aryl C-H trifluoromethylation, but the generation of CF3· from TFA may prove useful in other contexts and could potentially be extended to other trifluoromethylation reactions.
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http://dx.doi.org/10.1021/ol503189j | DOI Listing |
Inorg Chem
January 2025
Department of Chemistry, Virginia Tech, Blacksburg, Virginia 24061, United States.
Herein, we investigate the effects of ligand design on the nuclearity and reactivity of metal-ligand multiply bonded (MLMB) complexes to access an exclusively bimetallic reaction pathway for C-H bond functionalization. To this end, the diiron alkoxide [Fe(Dbf)] () was treated with 3,5-bis(trifluoromethyl)phenyl azide to access the diiron imido complex [Fe(Dbf)(μ-NCHF)] () that promotes hydrogen atom abstraction (HAA) from a variety of C-H and O-H bond containing substrates. A diiron bis(amide) complex [Fe(Dbf)(μ-NHCHF)(NHCHF)] () was generated, prompting the isolation of the analogous bridging amide terminal alkoxide [Fe(Dbf)(μ-NHCHF)(OCH)] () and the asymmetric pyridine-bound diiron imido [Fe(Dbf)(μ-NCHF)(NCH)] ().
View Article and Find Full Text PDFMolecules
December 2024
Institute of Organic and Analytical Chemistry (ICOA UMR 7311), CNRS, University of Orleans, F-45067 Orléans, France.
The emergence of RNA viruses driven by global population growth and international trade highlights the urgent need for effective antiviral agents that can inhibit viral replication. Nucleoside analogs, which mimic natural nucleotides, have shown promise in targeting RNA-dependent RNA polymerases (RdRps). Starting from protected 5-iodouridine, we report the synthesis of -substituted-(1,3-diyne)-uridines nucleosides and their phosphoramidate prodrugs.
View Article and Find Full Text PDFOrg Lett
January 2025
School of Chemistry and Chemical Engineering, Nanchang University, Nanchang, Jiangxi 330031, People's Republic of China.
A photocatalysis-involved α-amino radical provides an appealing approach for rapid construction of complex amine architectures. Reported herein is an organophotoredox catalytic approach to α-C-H alkylation and heteroarylation of benzyl anilines, which enables the introduction of valuable trifluoromethyl alcohol, chromanone, or pyridine motifs at the α position of amines. This protocol highlights metal-free, step and atom economies and broad substrate scopes (>80 examples).
View Article and Find Full Text PDFOrg Lett
December 2024
School of Pharmacy, Xi'an Jiaotong University, Xi'an, Shaanxi 710061, China.
J Am Chem Soc
December 2024
Departamento de Química and Laboratorio de Catálisis Homogénea, Unidad Asociada al CSIC, CIQSO-Centro de Investigación en Química Sostenible, Universidad de Huelva, Huelva 21007, Spain.
In this mixed computational and experimental study, we report a catalytic system for alkane C-C functionalization in which the responsible step for C-H bond activation shows no barrier in the potential energy path. DFT modeling of three silver-based catalysts and four diazo compounds led to the conclusion that the TpAg═C(H)CF (Tp = fluorinated trispyrazolylborate ligand) carbene intermediates interact with methane without a barrier in the potential energy surface, a prediction validated by experimentation using N═C(H)CF as the carbene source. The array of alkanes from propane to -hexane led to the preferential functionalization of the primary sites with unprecedented values of selectivity for an acceptor diazo compound.
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