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Insights for Organofluorine Chemistry – 2nd Edition

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Organic Chemistry".

Deadline for manuscript submissions: closed (1 December 2023) | Viewed by 1412

Special Issue Editor


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Guest Editor
1. College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou, China
2. State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou, China
Interests: organofluorine chemistry; fluorine-containing building blocks; fluoroheterocycles; fluoroalkylation; bioactive organofluorine compounds
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Special Issue Information

Dear Colleagues,

Organofluorine compounds have become increasingly important in human life. They have been widely used in pharmaceuticals, agrochemicals and material science due to their improved properties in comparison to their parent molecules, such as high lipophilicity, improved stability, drastic changes in physical properties and enhanced bioactivities. To date, approximately 20–25% of commercial pharmaceuticals and 30% of commercial agrochemicals contain at least one fluorine atom in their molecules. These ratios are steadily increasing. For instance, more than 30% of drugs and 60% of pesticides registered in the past five years are fluorinated organic compounds. However, organofluorine compounds are very scarce in nature. Only 13 naturally occurring organofluorine compounds have been found, and the majority are higher homologues of fluoroacetic acid. Thus, any organofluorine compound used for academic studies or marketed as a pharmaceutical, agrochemical or advanced material has to be synthesized by humans.

In view of the significance of and demands for organofluorine compounds in our lives, chemists have developed many ingenious strategies to introduce the fluorine element into organic compounds. In addition to traditional methods, many versatile fluorine-containing reagents, such as Selectfluor, NFSI, Ruppert–Prakash reagent, Togni reagent, Umenoto reagent, Langlois reagent, Chen’s reagent (MFSDA) and many others, have been developed and applied in the synthesis of organofluorine compounds. The study and application of these fluorine-containing reagents have tremendously pushed forward the progress of fluorine chemistry. Furthermore, fluorine-containing building block strategies are additional protocols to access organofluorine compounds, and many cheap, stable and valuable fluorine-containing building blocks have been used in industry for the synthesis of bioactive organofluorine compounds and advanced materials. In spite of these, more effective and environmental green strategies are still needed, and more functional organofluorine compounds need to be developed.

This Special Issue is designed to gather any research papers on organofluorine chemistry, such as new synthetic strategies for organofluorine compounds; the development of new fluorine-containing pharmaceuticals, agrochemicals and materials; and studies on the special properties and bioactivities of organofluorine compounds.

Prof. Dr. Yulai Hu
Guest Editor

Manuscript Submission Information

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Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Molecules is an international peer-reviewed open access semimonthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2700 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • organofluorine compounds
  • fluorination
  • fluoroalkylation
  • fluorination reagents
  • fluoroalkylation reagents
  • fluorine building blocks
  • fluorine drugs
  • fluorine pesticides
  • fluorinated materials

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Published Papers (2 papers)

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Research

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11 pages, 1709 KiB  
Article
Molecular-Simulation–Inspired Synthesis of [6]-Prismane via Photoisomerisation of Octafluoro[2.2]paracyclophane
by Yoichi Hosokawa, Shuji Kajiya, Ayako Ohshima, Satoshi Kawata, Nobuhiro Ishida and Arimitsu Usuki
Molecules 2024, 29(4), 783; https://doi.org/10.3390/molecules29040783 - 08 Feb 2024
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Abstract
Prismanes have been attracting interest for nearly 50 years because of their geometric symmetry, highly strained structures, and unique applications due to their high carbon densities and bulky structures. Although [3]-, [4]-, and [5]-prismanes have been synthesised, [6]-prismanes and their derivatives remain elusive. [...] Read more.
Prismanes have been attracting interest for nearly 50 years because of their geometric symmetry, highly strained structures, and unique applications due to their high carbon densities and bulky structures. Although [3]-, [4]-, and [5]-prismanes have been synthesised, [6]-prismanes and their derivatives remain elusive. Herein, fluorine chemistry, molecular mechanics, molecular orbital package, and density functional theory calculations were used to design and implement the photoisomerisation of octafluoro[2.2]paracyclophane (selected based on the good overlap of its lowest unoccupied molecular orbitals and short distance between the benzene rings) into octafluoro-[6]-prismane. Specifically, a dilute solution of the above precursor in CH3CN/H2O/dimethyl sulfoxide (DMSO) (2:1:8, v/v/v) solution was irradiated with ultraviolet light, with the formation of the desired product confirmed through the use of nuclear magnetic resonance spectroscopy and gas chromatography–mass spectrometry. The product was thermally stable in solution but not under work-up conditions, which complicated the further analysis and single-crystal preparation. The key criteria for successful photoisomerisation were the presence of fluorine substituents in the cyclophane structure and DMSO in the solvent system. A more stable derivative design requires the isolation of prismane products. The proposed fluorination-based synthetic strategy is applicable to developing novel high-strain molecules/materials with three-dimensional skeletons. Full article
(This article belongs to the Special Issue Insights for Organofluorine Chemistry – 2nd Edition)
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Review

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45 pages, 10444 KiB  
Review
Asymmetric α-Fluoroalkyl-α-Amino Acids: Recent Advances in Their Synthesis and Applications
by Nathan Picois, Yazid Boutahri, Pierre Milbeo, Chiara Zanato, Nathalie Lensen, Grégory Chaume and Thierry Brigaud
Molecules 2024, 29(6), 1408; https://doi.org/10.3390/molecules29061408 - 21 Mar 2024
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Abstract
Due to the specific properties provided by fluorine atoms to biomolecules, amino acids with fluorinated side chains are of great interest for medicinal chemistry and chemical biology. Among them, α-fluoroalkyl-α-amino acids constitute a unique class of compounds. In this review, we outline the [...] Read more.
Due to the specific properties provided by fluorine atoms to biomolecules, amino acids with fluorinated side chains are of great interest for medicinal chemistry and chemical biology. Among them, α-fluoroalkyl-α-amino acids constitute a unique class of compounds. In this review, we outline the strategies adopted for their syntheses in enantiopure or enantioenriched forms and their incorporation into peptides. We then describe the consequences of the introduction of fluorine atoms in these compounds for the modulation of their hydrophobicity and the control of their conformation. Emerging applications are presented in the areas of enzyme inhibition, medicinal chemistry, hydrolytic stability of peptides, antimicrobial peptides, PET, and 19F NMR probes. Full article
(This article belongs to the Special Issue Insights for Organofluorine Chemistry – 2nd Edition)
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