An iron porphyrin-catalyzed -trifluoroethylation of anilines has been developed with 2,2,2-trifluoroethylamine hydrochloride as the fluorine source. This one-pot N-H insertion reaction is conducted cascade diazotization/-trifluoroethylation reactions. The developed transformation can afford a wide range of -trifluoroethylated anilines in good yields using readily available primary amines and secondary anilines as starting materials.
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http://dx.doi.org/10.1039/d1ra03379d | DOI Listing |
J Am Chem Soc
June 2024
Department of Spectroscopy and Catalysis, Institute for Molecules and Materials, Radboud University, Heyendaalseweg 135, 6525 AJ Nijmegen, The Netherlands.
Electrochemical steps are increasingly attractive for green chemistry. Understanding reactions at the electrode-solution interface, governed by kinetics and mass transport, is crucial. Traditional insights into these mechanisms are limited, but our study bridges this gap through an integrated approach combining voltammetry, electrochemical impedance spectroscopy, and electrospray ionization mass spectrometry.
View Article and Find Full Text PDFJ Am Chem Soc
July 2023
Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095, United States.
Quasi-classical molecular dynamics (MD) simulations were carried out to study the mechanism of iron porphyrin-catalyzed hydroxylation of ethylbenzene. The hydrogen atom abstraction from ethylbenzene by iron-oxo species is the rate-determining step, which generates the radical pair of iron-hydroxo species and the benzylic radical. In the subsequent radical rebound step, the iron-hydroxo species and benzylic radical recombine to form the hydroxylated product, which is barrierless on the doublet energy surface.
View Article and Find Full Text PDFJ Labelled Comp Radiopharm
August 2023
Environmental Health Science Laboratory, Sumitomo Chemical Co., Takarazuka, Hyogo, Japan.
Biomimetic oxidation using synthetic iron-porphyrin (F TPPFeCl) as a catalyst eliminated a xylene moiety of the fungicide mandestrobin, uniformly labeled with carbon-14 at the benzyl ring, to produce the corresponding radiolabeled metabolite 1. This reaction mechanism was investigated by identifying chemical structures of intermediate 5 and p-xyloquinone derivatives 6 and 7, as by-products. Optimization of reaction factors based on the mechanism improved the yield of 1 from mandestrobin up to 87%.
View Article and Find Full Text PDFJ Am Chem Soc
March 2023
Guangdong Key Laboratory of Chiral Molecule and Drug Discovery, School of Pharmaceutical Sciences, Sun Yat-sen University, Guangzhou 510006, China.
Iron porphyrin carbenes (IPCs) have been extensively recognized as the reactive intermediates in various iron porphyrin-catalyzed carbene transfer reactions. While donor-acceptor diazo compounds have been frequently used for such transformations, the structures and reactivities of donor-acceptor IPCs are less explored. To date, no crystal structures of donor-acceptor IPC complexes have been reported, and therefore, the involvement of IPC intermediacy for such transformations lacks direct evidence.
View Article and Find Full Text PDFJ Am Chem Soc
July 2022
Department of Chemistry, University of California, Berkeley, California 94720, United States.
Bicarbonate-based electrolytes are ubiquitous in aqueous electrochemical CO reduction, particularly in heterogenous catalysis, where they demonstrate improved catalytic performance relative to other buffers. In contrast, the presence of bicarbonate in organic electrolytes and its roles in homogeneous electrocatalysis remain underexplored. Here, we investigate the influence of bicarbonate on iron porphyrin-catalyzed electrochemical CO reduction.
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