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A visible-light-induced cascade radical fluoroalkylation/cyclization of -hydroxyaryl enaminones/2-(allyloxy)benzaldehydes with CFBr/1,2-dibromotetrafluoroethane in the presence of -Ir(ppy) and KHPO has been developed, which efficiently provides 3-fluoroalkyl-substituted chromone and chroman-4-one derivatives in good yields. In particular, the industrially available and low cost CFBr and 1,2-dibromotetrafluoroethane are used as fluoroalkyl reagents in this process, endowing the process with the potential to be used on a large scale. The mechanism was proposed based on the control experiments. The protocol also has the advantages of broad substrate scope and green energy source.
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http://dx.doi.org/10.1039/d5ob01148e | DOI Listing |
Org Biomol Chem
September 2025
College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou, Gansu, 730070, P. R. China.
A visible-light-induced cascade radical fluoroalkylation/cyclization of -hydroxyaryl enaminones/2-(allyloxy)benzaldehydes with CFBr/1,2-dibromotetrafluoroethane in the presence of -Ir(ppy) and KHPO has been developed, which efficiently provides 3-fluoroalkyl-substituted chromone and chroman-4-one derivatives in good yields. In particular, the industrially available and low cost CFBr and 1,2-dibromotetrafluoroethane are used as fluoroalkyl reagents in this process, endowing the process with the potential to be used on a large scale. The mechanism was proposed based on the control experiments.
View Article and Find Full Text PDFJ Am Chem Soc
July 2025
Beijing National Laboratory for Molecular Sciences, Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China.
Due to the invaluable properties of organofluorine compounds, incorporating a fluorinated unit has become necessary in pharmaceuticals, agrochemicals, and materials. However, achieving asymmetric fluorination such as trifluoromethylation through chemo- or biocatalysis has been a synthetic challenge. Here, we introduce a unique cooperative photoenzymatic catalysis for the enantioselective fluoroalkylation/cyclization cascade.
View Article and Find Full Text PDFJ Org Chem
March 2024
School of Chemistry & Chemical Engineering, Henan University of Technology, Zhengzhou 450001, P. R. China.
A photochemical approach toward RCOCF-substituted pyrrolo[1,2-]indolediones was developed by the radical cascade difluoroalkylation/cyclization reaction of unactivated 1-acryloyl-2-cyanoindoles with ethyl iododifluoroacetate or iododifluoramides under visible-light irradiation. This transition-metal- and photosensitizer-free protocol afforded diverse difluoroalkylated pyrrolo[1,2-]indolediones in moderate to good yields under mild reaction conditions. Most appealingly, the reaction can proceed smoothly under sunlight irradiation, which opens a new avenue toward difluoroalkylated pyrrolo[1,2-]indolediones.
View Article and Find Full Text PDFJ Org Chem
December 2020
Key Lab of Science and Technology of Eco-Textile, Ministry of Education, College of Chemistry, Chemical Engineering and Biotechnology, Donghua University, Shanghai 201620, China.
A transition-metal- and oxidant-free electrochemical strategy for radical fluoroalkylation of vinyl azides was developed. The reaction was carried out under mild conditions by using inexpensive and bench-stable RSONa (R = CF, CFH) as fluorination reagents. Depending on the starting material, both the electrochemical radical cyclization and dearomatization products could be obtained.
View Article and Find Full Text PDFOrg Lett
February 2016
Department of Chemistry and Applied Biosciences, Swiss Federal Institute of Technology, ETH Zürich , Vladimir-Prelog-Weg 2, CH-8093 Zürich, Switzerland.
A copper-catalyzed fluoroalkylation-cyclization sequence of alkenes and alkynes enables the synthesis of fluorinated tetra- and dihydroimidazopyridines in moderate to excellent yields within 1 h at 70 °C. This reaction, which is carried out using copper(I) acetate as the catalyst, makes use of a new class of functionalized tetrafluoroethyl reagents based on a hypervalent iodine scaffold.
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