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Insights for Organofluorine Chemistry
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Insights for Organofluorine Chemistry

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

Deadline for manuscript submissions: closed (1 May 2023) | Viewed by 15076

Special Issue Editor

Prof. Dr. Yulai Hu

E-Mail Website
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
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Organofluorine compounds 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 the 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. Those ratios are 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 compounds used for academic studies or marketed as a pharmaceutical, agrochemical or advanced material has to be synthesized by humans.

In view of the great importance 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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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

Related Special Issue

Published Papers (10 papers)

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Research

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12 pages, 2069 KiB  
Article
Synthesis of Near-Infrared-Absorbing Anionic Heptamethine Cyanine Dyes with Trifluoromethyl Groups
by Hiroki Masuoka, Yasuhiro Kubota, Toshiyasu Inuzuka and Kazumasa Funabiki
Molecules 2023, 28(12), 4650; https://doi.org/10.3390/molecules28124650 - 8 Jun 2023
Cited by 1 | Viewed by 1376
Abstract
A novel anionic heptamethine cyanine (HMC) dye with two trifluoromethyl groups that selectively absorb near-infrared light is synthesized. When contrasted with previously studied anionic HMC dyes with substituents such as methyl, phenyl, and pentafluorophenyl groups, the trifluoromethylated dye displays a red-shifted maximum absorption [...] Read more.
A novel anionic heptamethine cyanine (HMC) dye with two trifluoromethyl groups that selectively absorb near-infrared light is synthesized. When contrasted with previously studied anionic HMC dyes with substituents such as methyl, phenyl, and pentafluorophenyl groups, the trifluoromethylated dye displays a red-shifted maximum absorption wavelength (for instance, 948 nm in CH2Cl2) along with enhanced photostability. Furthermore, HMC dyes with broad absorption in the near-infrared region are synthesized by combining a trifluoromethylated anionic HMC dye with a cationic HMC dye as a counterion. Full article
(This article belongs to the Special Issue Insights for Organofluorine Chemistry)
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15 pages, 2113 KiB  
Article
Controllable Synthesis of Trifluoromethyl- or gem-Difluorovinyl-containing Analogues of Neonicotinoids by the Reaction of α-(Trifluoromethyl)styrenes with 2-Nitroimino-imidazolidine
by Jingjing He, Zhudi Sun, Yupian Deng, Ying Liu, Pai Zheng and Song Cao
Molecules 2023, 28(8), 3530; https://doi.org/10.3390/molecules28083530 - 17 Apr 2023
Cited by 4 | Viewed by 1262
Abstract
A simple and straightforward addition or defluorination of α-(trifluoromethyl)styrenes with 2-nitroimino-imidazolidine (2a), 2-(nitromethylene)imidazolidine (2b), 2-cyanoimino-thiazolidine (2c), and (E)-1-methyl-2-nitroguanidine (2d), in a controlled manner, was developed. The hydroamination of α-(trifluoromethyl)styrenes with 2a, 2b [...] Read more.
A simple and straightforward addition or defluorination of α-(trifluoromethyl)styrenes with 2-nitroimino-imidazolidine (2a), 2-(nitromethylene)imidazolidine (2b), 2-cyanoimino-thiazolidine (2c), and (E)-1-methyl-2-nitroguanidine (2d), in a controlled manner, was developed. The hydroamination of α-(trifluoromethyl)styrenes with 2a, 2b, 2c, and 2d was completed in the presence of DBN at room temperature within 0.5–6 h, affording structurally diverse β-trifluoromethyl-β-arylethyl analogues of neonicotinoids in moderate to good yields. The γ,γ-difluoro-β-arylallyl analogues of neonicotinoids were also successfully synthesized via defluorination of α-(trifluoromethyl)styrenes, with 2a and 2c using NaH as base at an elevated temperature together with a prolonged reaction time of 12 h. The method features simple reaction setup, mild reaction conditions, broad substrate scope, high functional group compatibility, and easy scalability. Full article
(This article belongs to the Special Issue Insights for Organofluorine Chemistry)
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13 pages, 4191 KiB  
Article
Synthesis and Performance Analysis of Green Water and Oil-Repellent Finishing Agent with Di-Short Fluorocarbon Chain
by Yanli Li, Yi Luo, Qinqin Wang, Wei Zou, Wenjiang Zheng, Xiaoyan Ma and Hu Yang
Molecules 2023, 28(8), 3369; https://doi.org/10.3390/molecules28083369 - 11 Apr 2023
Cited by 1 | Viewed by 1391
Abstract
A novel fluorine-containing water-repellent agent (OFAE-SA-BA) was designed and synthesized by emulsion copolymerization, which was used to replace the commercial long fluorocarbon chain water-repellent agent. To improve water repellency, the intermediate and monomer containing two short fluoroalkyl chains were successfully synthesized and characterized [...] Read more.
A novel fluorine-containing water-repellent agent (OFAE-SA-BA) was designed and synthesized by emulsion copolymerization, which was used to replace the commercial long fluorocarbon chain water-repellent agent. To improve water repellency, the intermediate and monomer containing two short fluoroalkyl chains were successfully synthesized and characterized by 1H NMR, 13C NMR and FT-IR, respectively. After being treated by the water-repellent agent, the surface chemical composition, molecular weight, thermal stability, surface morphology, wetting behavior, and durability of the modified cotton fabrics were characterized using X-ray photoelectron spectrophotometry (XPS), gel permeation chromatography (GPC), thermal degradation (TG), scanning electron microscopy (SEM), and video-based contact angle goniometry, respectively. The cotton fabric demonstrated water contact angle of 154.1°, both the water and oil repellency rating were grade 4. The durability of water repellency of the treated fabrics only decreased slightly after 30 times, which represented very good washing durability. The finishing agent did not affect the whiteness of the fabric. Full article
(This article belongs to the Special Issue Insights for Organofluorine Chemistry)
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9 pages, 2480 KiB  
Communication
Theoretical Study on the Origin of Abnormal Regioselectivity in Ring-Opening Reaction of Hexafluoropropylene Oxide
by Cui Yu, Yueqian Sang, Yao Li and Xiaosong Xue
Molecules 2023, 28(4), 1669; https://doi.org/10.3390/molecules28041669 - 9 Feb 2023
Viewed by 1535
Abstract
That nucleophiles preferentially attack at the less sterically hindered carbon of epoxides under neutral and basic conditions has been generally accepted as a fundamental rule for predicting the regioselectivity of this type of reaction. However, this rule does not hold for perfluorinated epoxides, [...] Read more.
That nucleophiles preferentially attack at the less sterically hindered carbon of epoxides under neutral and basic conditions has been generally accepted as a fundamental rule for predicting the regioselectivity of this type of reaction. However, this rule does not hold for perfluorinated epoxides, such as hexafluoropropylene oxide (HFPO), in which nucleophiles were found to attack at the more hindered CF3 substituted β-C rather than the fluorine substituted α-C. In this contribution, we aim to shed light on the nature of this intriguing regioselectivity by density functional theory methods. Our calculations well reproduced the observed abnormal regioselectivities and revealed that the unusual regiochemical preference for the sterically hindered β-C of HFPO mainly arises from the lower destabilizing distortion energy needed to reach the corresponding ring-opening transition state. The higher distortion energy required for the attack of the less sterically hindered α-C results from a significant strengthening of the C(α)-O bond by the negative hyperconjugation between the lone pair of epoxide O atom and the antibonding C-F orbital. Full article
(This article belongs to the Special Issue Insights for Organofluorine Chemistry)
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12 pages, 5914 KiB  
Article
Composite Coatings of AMg3 Alloy Formed by a Combination of Plasma Electrolytic Oxidation and Fluoropolymer Spraying
by Dmitry V. Mashtalyar, Konstantine V. Nadaraia, Igor M. Imshenetskiy, Evgeniy A. Belov, Mariia S. Gerasimenko, Sergey L. Sinebryukhov and Sergey V. Gnedenkov
Molecules 2023, 28(2), 465; https://doi.org/10.3390/molecules28020465 - 4 Jan 2023
Cited by 2 | Viewed by 1046
Abstract
This paper presents the results of an investigation of the changes in the corrosion, wear resistance, and wettability of composite coatings formed on the AMg3 alloy through plasma electrolytic oxidation (PEO) and subsequent spraying with an organofluorine polymer. The evaluation of the electrochemical [...] Read more.
This paper presents the results of an investigation of the changes in the corrosion, wear resistance, and wettability of composite coatings formed on the AMg3 alloy through plasma electrolytic oxidation (PEO) and subsequent spraying with an organofluorine polymer. The evaluation of the electrochemical properties of the composite layers revealed a decrease in the corrosion current density compared with the PEO coating (from 3.8 × 10−8 to 3.1 × 10−11 A/cm2). The analysis of the wear resistance of composite coatings established that the application of this type of coating reduced the wear of the samples by two orders of magnitude when compared with the PEO layer. Using the contact-angle measurement, it was found that with an increase in the number of polymer spray applications, the wettability of coatings decreased, so the contact angle for the composite coating with triple fluoropolymer application increased by 134.3° compared to the base PEO coating. Full article
(This article belongs to the Special Issue Insights for Organofluorine Chemistry)
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9 pages, 1653 KiB  
Article
Visible Light Promotes Cascade Trifluoromethylation/Cyclization, Leading to Trifluoromethylated Polycyclic Quinazolinones, Benzimidazoles and Indoles
by Ransong Ma, Yuanyuan Ren, Zhoubin Deng, Ke-Hu Wang, Junjiao Wang, Danfeng Huang, Yulai Hu and Xiaobo Lv
Molecules 2022, 27(23), 8389; https://doi.org/10.3390/molecules27238389 - 1 Dec 2022
Cited by 5 | Viewed by 1536
Abstract
Efficient visible-light-induced radical cascade trifluoromethylation/cyclization of inactivated alkenes with CF3Br, which is a nonhygroscopic, noncorrosive, cheap and industrially abundant chemical, was developed in this work, producing trifluoromethyl polycyclic quinazolinones, benzimidazoles and indoles under mild reaction conditions. The method features wide functional [...] Read more.
Efficient visible-light-induced radical cascade trifluoromethylation/cyclization of inactivated alkenes with CF3Br, which is a nonhygroscopic, noncorrosive, cheap and industrially abundant chemical, was developed in this work, producing trifluoromethyl polycyclic quinazolinones, benzimidazoles and indoles under mild reaction conditions. The method features wide functional group compatibility and a broad substrate scope, offering a facile strategy to pharmaceutically produce valuable CF3-containing polycyclic aza-heterocycles. Full article
(This article belongs to the Special Issue Insights for Organofluorine Chemistry)
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8 pages, 2237 KiB  
Article
Reagent-Controlled Highly Stereoselective Difluoromethylation: Efficient Access to Chiral α-Difluoromethylamines from Ketimines
by Qinghe Liu, Taige Kong, Chuanfa Ni and Jinbo Hu
Molecules 2022, 27(20), 7076; https://doi.org/10.3390/molecules27207076 - 20 Oct 2022
Cited by 1 | Viewed by 1457
Abstract
A reagent-controlled highly stereoselective reaction between (S)-difluoromethyl phenyl sulfoximine 1 and imines is reported, and this synthetic method provides a variety of enantiomerically enriched α-difluoromethyl amines. The main pros of this approach include high efficiency, high stereoselectivity, and a broad substrate scope, which [...] Read more.
A reagent-controlled highly stereoselective reaction between (S)-difluoromethyl phenyl sulfoximine 1 and imines is reported, and this synthetic method provides a variety of enantiomerically enriched α-difluoromethyl amines. The main pros of this approach include high efficiency, high stereoselectivity, and a broad substrate scope, which is probably achieved through a non-chelating transition state. Full article
(This article belongs to the Special Issue Insights for Organofluorine Chemistry)
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11 pages, 1370 KiB  
Article
Synthesis of Trifluoromethylated Monoterpene Amino Alcohols
by Polina A. Petrova, Denis V. Sudarikov, Larisa L. Frolova, Roman V. Rumyantcev, Svetlana A. Rubtsova and Aleksandr V. Kutchin
Molecules 2022, 27(20), 7068; https://doi.org/10.3390/molecules27207068 - 20 Oct 2022
Cited by 1 | Viewed by 1283
Abstract
For the first time, monoterpene trifluoromethylated β-hydroxy-benzyl-O-oximes were synthesized in 81–95% yields by nucleophilic addition of the Ruppert–Prakash reagent (TMSCF3) to the corresponding β-keto-benzyl-O-oximes based on (+)-nopinone, (−)-verbanone and (+)-camphoroquinone. Trifluoromethylation has been determined to entirely proceed [...] Read more.
For the first time, monoterpene trifluoromethylated β-hydroxy-benzyl-O-oximes were synthesized in 81–95% yields by nucleophilic addition of the Ruppert–Prakash reagent (TMSCF3) to the corresponding β-keto-benzyl-O-oximes based on (+)-nopinone, (−)-verbanone and (+)-camphoroquinone. Trifluoromethylation has been determined to entirely proceed chemo- and stereoselective at the C=O rather than C=N bond. Trifluoromethylated benzyl-O-oximes were reduced to the corresponding α-trifluoromethyl-β-amino alcohols in 82–88% yields. The structure and configuration of the compounds obtained have been established. Full article
(This article belongs to the Special Issue Insights for Organofluorine Chemistry)
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10 pages, 3393 KiB  
Article
Regioselective Synthesis of 5-Trifluoromethyl 1,2,4-Triazoles via [3 + 2]-Cycloaddition of Nitrile Imines with CF3CN
by Bo Lin, Zipeng Zhang, Yunfei Yao, Yi You and Zhiqiang Weng
Molecules 2022, 27(19), 6568; https://doi.org/10.3390/molecules27196568 - 4 Oct 2022
Cited by 6 | Viewed by 1726
Abstract
We herein describe a general approach to 5-trifluoromethyl 1,2,4-triazoles via the [3 + 2]-cycloaddition of nitrile imines generated in situ from hydrazonyl chloride with CF3CN, utilizing 2,2,2-trifluoroacetaldehyde O-(aryl)oxime as the precursor of trifluoroacetonitrile. Various functional groups, including alkyl-substituted hydrazonyl chloride, [...] Read more.
We herein describe a general approach to 5-trifluoromethyl 1,2,4-triazoles via the [3 + 2]-cycloaddition of nitrile imines generated in situ from hydrazonyl chloride with CF3CN, utilizing 2,2,2-trifluoroacetaldehyde O-(aryl)oxime as the precursor of trifluoroacetonitrile. Various functional groups, including alkyl-substituted hydrazonyl chloride, were tolerated during cycloaddition. Furthermore, the gram-scale synthesis and common downstream transformations proved the potential synthetic relevance of this developed methodology. Full article
(This article belongs to the Special Issue Insights for Organofluorine Chemistry)
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Review

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28 pages, 10557 KiB  
Review
Versatile Fluorine-Containing Building Blocks: β-CF3-1,3-enynes
by Mingqing Liu, Zongxiang Yu, Jingtong Li and Yuanjing Xiao
Molecules 2022, 27(24), 9020; https://doi.org/10.3390/molecules27249020 - 17 Dec 2022
Cited by 6 | Viewed by 1631
Abstract
The development of diversity-oriented synthesis based on fluorine-containing building blocks has been one of the hot research fields in fluorine chemistry. β-CF3-1,3-enynes, as one type of fluorine-containing building blocks, have attracted more attention in the last few years due to [...] Read more.
The development of diversity-oriented synthesis based on fluorine-containing building blocks has been one of the hot research fields in fluorine chemistry. β-CF3-1,3-enynes, as one type of fluorine-containing building blocks, have attracted more attention in the last few years due to their distinct reactivity. Numerous value-added trifluoromethylated or non-fluorinated compounds which have biologically relevant structural motifs, such as O-, N-, and S-heterocycles, carboncycles, fused polycycles, and multifunctionalized allenes were synthesized from these fluorine-containing building blocks. This review summarizes the most significant developments in the area of synthesis of organofluorine compounds based on β-CF3-1,3-enynes, providing a detailed overview of the current state of the art. Full article
(This article belongs to the Special Issue Insights for Organofluorine Chemistry)
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