Quantum chemical calculation of 19F NMR chemical shifts of trifluoromethyl diazirine photoproducts and precursors

Raimer, Björn; Jones, Peter G.; Lindel, Thomas

doi:10.1016/j.jfluchem.2014.06.027

Cited by 18 publications

(7 citation statements)

References 28 publications

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“…It should also be recalled that in the paper by Raimer et al, [ 48 ] an average accuracy of 2.9 ppm (standard deviation) was achieved in the B3LYP/6‐311G++(2 d ,2 p ) calculations of the 19 F NMR chemical shifts followed by a Boltzmann weighting of the optimized conformers in the series of 30 compounds investigated both experimentally and theoretically. The average deviation of the calculated from the experimental values corresponded to only about 1% of the standard 19 F NMR chemical shift range.…”

Section: Resultsmentioning

confidence: 96%

Computational ¹⁹F NMR of trifluoromethyl derivatives of alkenes, pyrimidines, and indenes

Ukhanev

Федоров

Krivdin

2023

Magnetic Reson in Chemistry

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The 19F NMR chemical shifts of 13 trifluoromethyl derivatives of alkenes, pyrimidines, and indenes were calculated at the DFT level using the BhandHLYP, BHandH, PBE, PBE0, O3LYP, B3LYP, KT2, and KT3 functionals in combination with the pcS‐2 basis set. Best result was documented for the BHandHLYP functional: The mean absolute error (MAE) of 0.66 ppm for the scaled values was achieved for the range of about 20 ppm. Solvent, vibrational, and relativistic corrections were found to be rather small, especially when taken in combination, generally demonstrating a slight decrease in the difference between calculated and experimental fluorine chemical shifts. As a measure of the practical importance of these compounds, one should recall that the growing number of life science products that contain trifluoromethyl groups provides a continuing driving force for the development of an effective methodology that enables both regio‐ and stereoselective introduction of trifluoromethyl groups into both aliphatic and aromatic systems.

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Section: Resultsmentioning

confidence: 96%

Computational ¹⁹F NMR of trifluoromethyl derivatives of alkenes, pyrimidines, and indenes

Ukhanev

Федоров

Krivdin

2023

Magnetic Reson in Chemistry

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“…Theoretically, the relevant atoms were calculated to range between -66.77 and -99.08 ppm using C6F6 as a reference. To calculate theoretical chemical shifts of MITPIM, δ = σref -σ + δref (σref = 333.6 ppm, δref = -164.9 ppm, σ = calculated shift) equation was used [42]. The data were shown in Table 3, experimental and theoretical spectra were given in Figures 6 and 7 A correlation between theoretical and experimental NMR chemical shift values was examined, and it was found that theoretical predictions and experimental data showed a good agreement [25], [43][44][45].…”

Section: Nmr Spectramentioning

confidence: 99%

Imidazole Based Novel Schiff Base: Synthesis, Characterization, Quantum Chemical Calculations, In Silico Investigation of ADMEt Properties and Molecular Docking Simulations against VEGFR2 Protein

Dilek

2024

Bitlis Eren Üniversitesi Fen Bilimleri Dergisi

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The potential drug candidate novel Schiff base, 2-(((3-(4-methyl-1H-imidazol-1-yl)-5-(trifluoromethyl)phenyl)imino)methyl)phenol (MITPIM) was synthesized by the reaction of salicylaldehyde and 3-(4-methyl-1H-imidazol-1-yl)-5-(trifluoromethyl)aniline which is the precursor of the nilotinib molecule used in the cancer treatment. It was characterizated by using spectroscopic techniques such as 1H-NMR, 13C-NMR, 19F-NMR, FT-IR and UV-Vis. DFT computational technique was used for further investigation. DFT/B3LYP method and the 6-311G(d,p) basis set were used to determine optimized geometry. Then by using optimized geometry and DFT approach three-dimensional molecular electrostatic potential (MEP), vibration frequencies, NMR chemical shift values, HOMOs-LUMOs and molecular orbital energies were calculated. It was observed that the experimental and theoretical datas were in good agreement. The ADME and toxicity properties were investigated by using online servers. According to the results, it was concluded that the MITPIM has low toxicity and high oral bioavailability. Molecular docking simulations of the MITPIM with VEGFR2 protein (PDB ID: 2XIR) were investigated. According to molecular docking studies, the binding energy of the complex formed by the MITPIM with VEGFR2 protein (PDB ID: 2XIR) was −9.34 kcal/mol and the value was close to nilotinib’s binding score which was -9.69 kcal/mol. Molecular docking and ADMEt results shown that the newly synthesized MITPIM has the potential to be drug.

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“…The smallest deviation was found for ωB97XD/TApr-cc-pVDZ (Δδ calc-exp 3.2 ppm (4-F) and 0.0 ppm (7-F)), which was used for all further calculations. The B3LYP/6-311 + G(d,p) calculation, which had shown good accuracy for trifluoromethyldiazirines, [16] showed higher deviations (Δδ calc-exp À 7.8 ppm (4-F) and À 3.6 ppm (7-F)). The highest averaged deviations between calculated and experimental values were observed for 5-F of the 5,7-difluorinated (Δδ calc-exp + 4.8 ppm) and 4-F of the 4,7-difluorinated (Δδ calc-exp + 4.0 ppm) adducts.…”

Section: Predictability Of the 19 F Nmr Chemical Shiftsmentioning

confidence: 99%

Di‐ and Trifluorinated 2‐Azidobenzimidazole Derivatives: Synthesis, Photooxygenation, and ¹⁹F NMR Prediction

et al. 2021

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The photoreactivity of a series of hitherto unknown, multiply fluorinated 2-azidobenzimidazole derivatives was investigated. The synthesis of the starting material includes regioselective pdefluorination of nitrobenzene derivatives employing Ogoshi's conditions. If the 6-position was unsubstituted, irradiation in the presence of N-protected amino acids at 300 nm (Rayonet) led to the formation of arylesters by oxygenation of the 6position in good to excellent yields and perfect regioselectivity. We did not observe any displacement of fluoride. If the 6position itself was fluorinated, alternative positions of the benzene portion were attacked. Mechanistically, the reaction proceeds through ring opening of the singlet nitrene to the cyanodiimine or via the iminobenzimidazolium ion. The availability of a set of fluorinated photo-adducts prompted the quantum chemical calculation of their 19 F NMR chemical shifts. Even with the most suitable method investigated (ωB97XD/ TApr-cc-pVDZ), deviations of up to 5 ppm from the experimental values were observed, underlining the importance of experimental measurements.

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Quantum chemical calculation of 19F NMR chemical shifts of trifluoromethyl diazirine photoproducts and precursors

Cited by 18 publications

References 28 publications

Computational ¹⁹F NMR of trifluoromethyl derivatives of alkenes, pyrimidines, and indenes

Computational ¹⁹F NMR of trifluoromethyl derivatives of alkenes, pyrimidines, and indenes

Imidazole Based Novel Schiff Base: Synthesis, Characterization, Quantum Chemical Calculations, In Silico Investigation of ADMEt Properties and Molecular Docking Simulations against VEGFR2 Protein

Di‐ and Trifluorinated 2‐Azidobenzimidazole Derivatives: Synthesis, Photooxygenation, and ¹⁹F NMR Prediction

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Quantum chemical calculation of 19F NMR chemical shifts of trifluoromethyl diazirine photoproducts and precursors

Cited by 18 publications

References 28 publications

Computational 19F NMR of trifluoromethyl derivatives of alkenes, pyrimidines, and indenes

Computational 19F NMR of trifluoromethyl derivatives of alkenes, pyrimidines, and indenes

Imidazole Based Novel Schiff Base: Synthesis, Characterization, Quantum Chemical Calculations, In Silico Investigation of ADMEt Properties and Molecular Docking Simulations against VEGFR2 Protein

Di‐ and Trifluorinated 2‐Azidobenzimidazole Derivatives: Synthesis, Photooxygenation, and 19F NMR Prediction

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Computational ¹⁹F NMR of trifluoromethyl derivatives of alkenes, pyrimidines, and indenes

Computational ¹⁹F NMR of trifluoromethyl derivatives of alkenes, pyrimidines, and indenes

Di‐ and Trifluorinated 2‐Azidobenzimidazole Derivatives: Synthesis, Photooxygenation, and ¹⁹F NMR Prediction