New fluorinated 3,6-dihydropyridines were obtained by the electrophilic fluorination of 1,2-dihydropyridines with Selectfluor. These 3-fluoro-3,6-dihydropyridines were easily converted to corresponding pyridines by the elimination of hydrogen fluoride under mild conditions. A new approach to the synthesis of methyl 2-(fluoromethyl)-5-nitro-6-arylnicotinates by the fluorination of 3-fluoro-2-methyl-5-nitro-3,6-dihydropyridines or 1,2-dihydropyridines with Selectfluor has been developed.
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http://dx.doi.org/10.3390/molecules25143143 | DOI Listing |
Angew Chem Int Ed Engl
December 2024
School of Chemistry, Trinity College Dublin, The University of Dublin, College Green, Dublin 2, Ireland.
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 Co(OTf) (10 mol% catalyst; OTf=trimfluoromethanesulfonate) in combination with polydentate N-donor ligands (e.
View Article and Find Full Text PDFJ Inorg Biochem
February 2025
EaStCHEM School of Chemistry, Joseph Black Building, Kings Buildings, University of Edinburgh, David Brewster Road, Edinburgh EH9 3FJ, UK. Electronic address:
Biocatalysts for fluorination are rare, and thus of great interest for artificial enzyme design. Biohybrid catalysts including Cu-based DNAzymes and dinucleotide catalysts can catalyse enantioselective electrophilic fluorination of β-ketoesters. Here we report the investigation of Cu-based artificial metalloenzymes as catalysts for electrophilic fluorination reactions.
View Article and Find Full Text PDFChem Sci
December 2024
College of Chemistry, Pingyuan Laboratory, Zhengzhou University 100 Science Avenue Zhengzhou 450001 Henan China
Herein, we demonstrate a practical dual ligand-enabled iron photocatalysis paradigm-converting all kinds of halogen-containing carboxylates (C X COO, X: F, Cl, Br) into C X radicals for the valuable chloro/fluoro-polyhaloalkylation of non-activated alkenes with easily available trichloroacetonitrile/Selectfluor as the electrophilic halogenation reagent. The modular assembly of the effective iron and C X COO-based light-harvesting species using the two ligands-OMe/CF-substituted bipyridine and acetonitrile/trichloroacetonitrile is evidenced by detailed mechanistic studies. The late-stage modification, low loading amount of iron (TON: 257) and feasible gram-scale synthesis show the utility of this protocol.
View Article and Find Full Text PDFJ Am Chem Soc
November 2024
Organisch-Chemisches Institut, Universität Münster, 48149 Münster, Germany.
Organofluorine compounds, including fluorinated pyridines and isoquinolines, play a crucial role in pharmaceuticals, agrochemicals, and materials science. However, step-economic selective C-H-functionalization to access these fluorinated azaarenes is still underexplored, with selective -C-H-fluorination proving to be especially elusive. Here we present a practical method for formal -C-H-fluorination of pyridines and isoquinolines.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
October 2024
Department of Chemistry, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, CA, 92037, USA.
Despite extensive efforts to develop γ-lactamization reactions for pyrrolidinone synthesis using either cyclometallation, C-H insertion, or radical C-H abstraction strategies, γ-lactamization reactions of aliphatic amides using practical catalysts and common protecting groups remain extremely rare. Herein we report copper-catalyzed γ-C(sp)-H lactamization and iminolactonization of tosyl-protected aliphatic amides using inexpensive Selectfluor as the sole oxidant. A switchable selectivity of γ-lactams or γ-iminolactones can be obtained by using two different sets of reaction conditions.
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