• Title/Summary/Keyword: Fluorination

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Photodegradation Characteristics of Oxygen Vacancy-fluorinated WO3 Photocatalysts Controlled by Plasma and Direct Vapor Fluorination (플라즈마 및 직접 기상 불소화에 의해 제어된 산소결핍 불소화 WO3 광촉매의 광분해 특성)

  • Lee, Hyeryeon;Lee, Raneun;Kim, Daesup;Lee, Young-Seak
    • Applied Chemistry for Engineering
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    • v.33 no.2
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    • pp.159-165
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    • 2022
  • To enhance the photocatalytic activities of WO3 photocatalysts, fluorine doping was performed to induce the oxygen vacancies. Both plasma and direct vaper fluorination were carried out for fluorine doping, and photocatalytic activities were examined by using methylene blue dye. Oxygen vacancies of the plasma and direct vaper fluorinated WO3 photocatalysts were measured to be 14.65 and 18.59%, which increased to about 23 and 56% at pristine WO3 photocatalysts. The degradation efficiency of methylene blue was also determined about 1.7 and 3.4 times higher than pristine WO3 photocatalysts, respectively, depending on oxygen vacancies increased. In addition, it was confirmed that the bandgap process energy decreased from 2.95 eV to 2.64 and 2.45 eV after fluorine doping. From this result, it is considered that the direct vaper fluorination has an advantage for increasing the photocatalytic activities of WO3 compared to that of the plasma fluorination.

Very Efficient Nucleophilic Aromatic Fluorination Reaction in Molten Salts: A Mechanistic Study

  • Jang, Sung-Woo;Park, Sung-Woo;Lee, Byoung-Se;Chi, Dae-Yoon;Song, Choong-Eui;Lee, Sung-Yul
    • Bulletin of the Korean Chemical Society
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    • v.33 no.3
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    • pp.881-884
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    • 2012
  • We report a quantum chemical study of an extremely efficient nucleophilic aromatic fluorination in molten salts. We describe that the mechanism involves solvent anion interacting with the ion pair nucleophile $M^+F^-$(M = Na, K, Rb, Cs) to accelerate the reaction. We show that our proposed mechanism may well explain the excellent efficiency of molten salts for SNAr reactions, the relative efficacy of the metal cations, and also the observed large difference in rate constants in two molten salts $(n-C_4H_9)_4N^+\;CX_3SO_3^-$, (X=H, F) with slightly different sidechain ($-CH_3$ vs. $-CF_3$).

Development of fluorination methodology for carbon-fluorine bond formation: nucleophilic fluorinating reagents in the mid-2000s

  • Bae, Dae Young;Lee, Eunsung
    • Journal of Radiopharmaceuticals and Molecular Probes
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    • v.3 no.2
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    • pp.129-133
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    • 2017
  • Since carbon-fluorine (C-F) bonds play a key role to improve bioavailability and lipophilicity, they have found commonly in pharmaceuticals, radiopharmaceuticals, agrochemicals, and material science. Advances on the efficient method to introduce fluorine to complex organic molecules are mainly results of development of fluorination reagents and transition metal catalysts. In this mini-review, we want to emphasize two representative nucleophilic fluorinating reagents regarding carbon-fluorine bond formation, which were developed in the mid-2000s.

Catalytic Enantioselective Fluorination Reactions of α-Cyano Acetates and α-Cyanophosphonates Using Chiral Palladium Complexes

  • Kim, Sun-Mi;Kang, Young-Ku;Cho, Min-Je;Mang, Joo-Yang;Kim, Dae-Young
    • Bulletin of the Korean Chemical Society
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    • v.28 no.12
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    • pp.2435-2441
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    • 2007
  • The catalytic enantioselective electrophilic fluorinations of active methane compounds promoted chiral palladium complexes have been developed. Treatment of α-cyano acetates and α-cyanoalkylphosphonates with N-fluorobenzenesulfonimide as the fluorine source under mild reaction conditions afforded the corresponding α-cyano-α-fluorinated adducts in high yields with excellent enantiomeric excesses (up to 99% ee). These reactions can be conducted in alcoholic solvents without any precaution to exclude water and moisture.

Synthesis and Antiviral Activity of $2^1$-Fluorohexopyranosyl Nucleosides

  • Jeong, Lak-Shin;Lee, Jong-Eun;Kim, Hea-Ok;Chun, Moon-Woo
    • Archives of Pharmacal Research
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    • v.21 no.3
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    • pp.338-343
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    • 1998
  • $2^1$-Fluorohexopyranosyl nucleosides 1a and 1b which contained a bioisosteric double bond and a fluorine were synthesized in 12 steps, starting from D-galactose. During diethylaminosulfur trifluoride (DAST) fluorination, retention of stereochemistry was observed through the participation of methoxy or chloro group at the 6-posiition of the purine base. The final nucleosides 1a and 1b were found to be inactive against HIV-1 and HSV-1,2.

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Enantioselective Fluorination of β-Keto Phosphonates and β-Ketoesters Catalyzed by Chiral Palladium Complexes

  • Lee, Na-Ri;Kim, Sun-Mi;Kim, Dae-Young
    • Bulletin of the Korean Chemical Society
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    • v.30 no.4
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    • pp.829-836
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    • 2009
  • The catalytic enantioselective electrophilic fluorinations of active methine compounds promoted chiral palladium complexes have been developed. Treatment of $\beta$-keto phosphonates and $\beta$-ketoesters with N-fluorobenzenesulfonimide as the fluorine source under mild reaction conditions afforded the corresponding $\alpha$-fluorinated adducts in high yields with excellent enantiomeric excesses (up to 99% ee). These reactions can be conducted in alcoholic solvents without any precaution to exclude water and moisture.

Theoretical study on electronic properties of deoxyfluorinating sulfur-based reagents

  • Lim, Soobin;Lee, Eunsung
    • Journal of Radiopharmaceuticals and Molecular Probes
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    • v.2 no.1
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    • pp.51-55
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    • 2016
  • Organofluorine compounds have become increasingly important as pharmaceuticals, radiopharmaceuticals, agrochemicals, and material science. Recent advances on the efficient introduction of fluorine to organic molecules are mainly results of development of transition metal catalysts and fluorination reagents. Among the various fluorination reagents, we have been interested in developing more efficient sulfur-based deoxyfluorinating reagents. Here we report various electronic properties of five popular sulfur-based deoxyfluorinating reagents using density functional theory calculation. We believe that the theoretical study on the reagents will assist the rational design of new deoxyfluorinating reagents.