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Visible light photocatalytic cross-coupling and addition reactions of arylalkynes with perfluoroalkyl iodides have been developed. Through slight modifications of the reaction conditions, reactions that are selective for the preparation of the C-C coupling product (perfluoroalkyl alkynes) and the addition products (iodo-perfluoroalkyl substituted alkenes) can be achieved. These reactions work well with different types of alkynes and perfluoroalkyl iodides. As the iodide generated from the reaction can serve as a reductant to regenerate the photocatalyst from its oxidized form, no sacrificial electron donor is required.
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http://dx.doi.org/10.1039/d0ob01767a | DOI Listing |
Nat Commun
August 2025
State Key Laboratory of Fluorine and Nitrogen Chemistry and Advanced Materials, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Ling-Ling Road, Shanghai, 200032, China.
Branched PFOA and PFOS have shorter half-lives, lower toxicity, and weaker serum protein binding than linear ones, offering better environmental and health safety. Yet methods to access such branched motifs remain under developed. We now introduce a one-step dehydroxy-perfluoro-tert-butylation of alcohols, in which perfluoro-tert-butyl phenyl sulfone serves both to activate the C-O bond and to deliver the perfluoro-tert-butyl group.
View Article and Find Full Text PDFOrg Biomol Chem
August 2025
School of Chemistry and Chemical Engineering, Linyi University, Linyi 276000, P. R. China.
Perfluoroalkyl-functionalized heterocycles exhibit profoundly modified bioactivities, motivating the development of efficient methods for precise perfluoroalkyl group installation. A new metal-free photoinduced radical-initiated cascade reaction was developed for the rapid synthesis of perfluoroalkyl-substituted iminoisobenzofurans by reacting various perfluoroalkyl iodides (R-I) under mild reaction conditions. In this reaction system, the formation of electron donor-acceptor (EDA) complexes is pivotal for the visible-light promoted transformation in the absence of additional photocatalytic species.
View Article and Find Full Text PDFToxics
June 2025
Center for Computational Toxicology and Exposure, Office of Research and Development, U.S. Environmental Protection Agency, Durham, NC 27709, USA.
Some PFASs are immunotoxic in rodent models and associated with diminished vaccine response in exposed humans. This study assessed the immunotoxicity of four PFASs via the T cell-dependent IgM antibody response (TDAR) to sheep red blood cells (SRBCs) in adult male rats following 28-day oral repeat dosing. The PFASs included 1H,1H,9H-perfluorononyl acrylate (PFNAC), 1H,1H,2H,2H-perfluorohexyl iodide (PFHI), 2-chlorotetrafluoropropionic acid (CTFPA), and 3,3,4,4,5,5,5-heptafluoropentan-2-one (MHFPK), administered in corn oil.
View Article and Find Full Text PDFJ Org Chem
April 2025
Technical Institute of Fluorochemistry, School of Chemistry and Molecular Engineering, Nanjing Tech University, Nanjing 211816, China.
Perfluoroalkyl alkenyl iodides (PFAIs) are emerging as highly reactive, storage-stable, and multifunctional fluoroalkyl-bearing reagents, facilitating the manufacture of value-added organofluorides through multi-halo-functionalization. Herein, we developed a water-involved 1,3-aminoxylation of PFAIs with sulfonamides for the chemo-, regio-, and -stereoselective synthesis of valuable β-fluoroacyl vinylamines. This reaction proceeded via a sequential deiodoamination and defluoroxylation process under transition-metal-free conditions, featuring a broad substrate scope and good functional group tolerance.
View Article and Find Full Text PDFOrg Lett
February 2025
Hebei Normal University for Nationalities, Chengde, Hebei 067000, China.
A new three-component 1,2-perfluoroalkyl trifluoromethylthiolation of alkenes via dual photoredox/copper catalysis has been established, affording a variety of CF/CFS-containing molecules under mild conditions in a redox-neutral manner. This protocol exhibits excellent functional group tolerance, broad compatibility with various alkenes and perfluoroalkyl iodides, and potential utility in the modification of bioactive molecules.
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