C−F Bond Activation and Functionalizations Enabled by Metal‐free NHCs and Their Metal Complexes

Muthuvel, Karthick; Gandhi, Thirumanavelan

doi:10.1002/cctc.202101579

Cited by 20 publications

(20 citation statements)

References 94 publications

(131 reference statements)

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“…The reaction of 1g (0.106 g, 1 mmol) and Ag 2 O (0.46 g, 2 mmol) led to the desired 2g complex 2g as a white powder (0.1 g, 80%). 1 H NMR (300 MHz, CDCl 3 ) 13…”

Section: Chloro[13-bis (Ethylmorpholine)benzimidazol-2-yliden] Silver...mentioning

confidence: 99%

“…The Ag-NHC and Au-NHC complexes were synthesized in the dark. 1 H and 13 C NMR spectra were recorded by a Bruker Avance III HD 300 or 400 or 600 MHz NMR spectrometer. The Q-TOF/LCMS analysis was recorded by an Agilent 6530 Accurate-Mass Q-TOF LC/MS spectrometer.…”

Section: General Considerationsmentioning

confidence: 99%

“…M-NHC complexes are more stable toward the air, moisture, and harsh reaction conditions in many applications. [5,[8][9][10][11][12][13] Effortless modification of the NHC ligand via N 1 and N 3 positions is essential, while N-substituents significantly affect the reactivity of NHC and binding. Different functional groups as N-substituents can be introduced depending on the purpose to provide selectivity or reactivity.…”

Section: Introductionmentioning

confidence: 99%

“…Different M-NHC complexes have been studied, mainly catalysis as a catalyst. [5,[8][9][10][11][12][13] However, M-NHC complexes have been used as antibacterial, antifungal, and especially anticancer and arthritis agents. [3,4,6,7,[14][15][16][17][18][19][20] In the beginning, NHC ligands were used as auxiliary ligands to replace toxic phosphines ligands.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis and biological evaluation of Au‐NHC complexes

Ekinci

Akkoç

Khan

et al. 2022

Applied Organom Chemis

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New seven Au-N-heterocyclic carbene (NHC) complexes have been synthesized via transmetalation from Ag-NHC complexes. NHC salts, Ag-NHC, and Au-NHC complexes were fully characterized by widely used spectroscopic techniques. The molecular and crystal structures of 3b and 3f Au-NHC complexes were clarified through the single-crystal X-ray diffraction method.According to X-ray diffraction analysis results, the coordination geometry around Au(I) atoms in the complexes are revealed to be almost linear with C-Au-Cl angle. Anticancer activity, DNA binding, xanthine oxidase (XO) inhibitory activity studies, and molecular docking studies were evaluated for all Au-NHC complexes to explore the binding mechanism at the active site. The IC 50 value of Au-NHC complexes against human colorectal cancer (Caco-2) and breast cancer (MCF-7) cell lines was defined by MTT assay. The IC 50 values for MCF-7 in the range of 5.2 ± 2 to 152.4 ± 1 μM and Caco-2 5.2 ± 1 to 152.7 ± 2 μM showed that 3a, 3b, 3c, 3d, and 3g have better anticancer activity than Cisplatin incredibly complex 3a against both cancer cell line. All Au-NHC complexes showed excellent antimicrobial activity against different bacteria and fungi. 3a was the complex that exhibited the best antimicrobial activity here as well. The XO inhibitory activity experimental results indicated that all gold complexes showed remarkable inhibition activity against XO compared to the generally used standard, allopurinol. The range of IC 50 value was determined from 0.407 to 2.681 μM. 3d complex showed the lowest IC50 value at 0.407 μM. DNA binding experiments were performed using agarose gel electrophoresis to observe the ability of synthesized Au-NHC complexes to interact with the supercoiled pUC19 plasmid DNA. Molecular docking studies were performed to determine the binding mode of all active compounds against the XO enzyme, antibacterial, antifungal, and MCF-7 cell lines.

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“…The reaction of 1g (0.106 g, 1 mmol) and Ag 2 O (0.46 g, 2 mmol) led to the desired 2g complex 2g as a white powder (0.1 g, 80%). 1 H NMR (300 MHz, CDCl 3 ) 13…”

Section: Chloro[13-bis (Ethylmorpholine)benzimidazol-2-yliden] Silver...mentioning

confidence: 99%

Section: General Considerationsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Synthesis and biological evaluation of Au‐NHC complexes

Ekinci

Akkoç

Khan

et al. 2022

Applied Organom Chemis

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“…In contrast to canonical equation ( 12), all trained methods were parametrized using metal-oxo oxidants and their transferability to a purely organic chemical space would be paramount as the field of organocatalysis continues to bloom. 36,37,38 The predictions from the four models on the organic test set are condensed in Figure 7. Borovik's model, adapted to the prediction of relative HAA barriers, displays two parameters, (α,…”

Section: Most Of the Points Of The Mayer Set Inmentioning

confidence: 99%

H-atom Abstraction Reactivity through the Lens of Asynchronicity and Frustration with their Counter-Acting Effects on Barriers

Maldonado-Domínguez

Srnec

2022

Preprint

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Hydrogen atom abstraction (HAA) is central to life and its importance in synthetic chemistry continues to grow. Enzymes rely on HAA to trigger life-sustaining reaction cascades, and greener synthetic routes are attainable by in situ capture of the carbon-centered radicals generated by HAA. Despite the potential of HAA for the diversification of molecular complexity and the late-stage functionalization of bioactive compounds, readily applicable and reliable models translating experimentally or computationally accessible thermodynamic quantities into relative free energy barriers are missing. In this work, we discovered a complete thermodynamic basis for the description of HAA reactivity, which consists of three components. Besides, the traditional linear free energy relationship and the recently introduced factor of asynchronicity (Srnec et al, PNAS 2018, 115, E10287-E10294), we present the third thermodynamic component of H-atom abstraction reactions – factor of frustration that arises from the dissimilarity of the species competing over a hydrogen atom in their overall ability to acquire electron and proton. Incorporating these non-classical descriptors into a Marcus-type model, the approach herein presented allows nearly quantitative prediction of relative barriers in six sets of metal-oxo-mediated HAA reactions, outperforming existing methods even in a stringent test with >200 computational HAA reactions.

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C–F Activation with Metal and Organocatalysts

Hamel,

Ferlet,

Chabaud

et al. 2024

PATAI'S Chemistry of Functional Groups

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Organofluorine compounds feature the strongest single bond to carbon: the CF bond. While generally considered inert, properly devised reaction conditions can lead to the selective cleavage of CF bonds, despite the presence of weaker bonds in the molecule. This chapter outlines the different catalytic reaction pathways that result in partial or exhaustive defluorination of fluorinated units. Throughout the chapter, the emphasis is put on the singular events that lead to CF bond cleavage, not on the methods themselves.

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C−F Bond Activation and Functionalizations Enabled by Metal‐free NHCs and Their Metal Complexes

Cited by 20 publications

References 94 publications

Synthesis and biological evaluation of Au‐NHC complexes

Synthesis and biological evaluation of Au‐NHC complexes

H-atom Abstraction Reactivity through the Lens of Asynchronicity and Frustration with their Counter-Acting Effects on Barriers

C–F Activation with Metal and Organocatalysts

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