Computational investigation of catalytic effects of CX3COOH (X = F,Cl,H) on the three-component cyclocondensation reaction

Abdullayev, Yusif; Sudjaev, Afsun; Autschbach, Jochen

doi:10.1007/s00894-019-4059-7

Cited by 7 publications

(2 citation statements)

References 30 publications

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“…Overall, for catalytic efficiency estimations, we used the energy span approximation using the Eyring equation [43][44][45] (See ESI). We calculated the turnover frequency (TOF) for the ligand included blue (trans) route in Figure 2 and compared the results with the ligand-free route.…”

Section: Resultsmentioning

confidence: 99%

Computational exploration of the copper(I)‐catalyzed conversion of hydrazones to dihalogenated vinyldiazene derivatives

Askerova,

Abdullayev,

Shikhaliyev

et al. 2024

J Comput Chem

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This computational study explores the copper (I) chloride catalyzed synthesis of (E)‐1‐(2,2‐dichloro‐1‐phenylvinyl)‐2‐phenyldiazene (2Cl‐VD) from readily available hydrazone derivative and carbon tetrachloride (CCl4). 2Cl‐VD has been extensively utilized to synthesize variety of heterocyclic organic compounds in mild conditions. The present computational investigations primarily focus on understanding the role of copper (I) and N1,N1,N2,N2‐tetramethylethane‐1,2‐diamine (TMEDA) in this reaction, TMEDA often being considered a proton scavenger by experimentalists. Considering TMEDA as a ligand significantly alters the energy barrier. In fact, it is only 8.3 kcal/mol higher compared to the ligand‐free (LF) route for the removal of a chlorine atom to form the radical ·CCl3 but the following steps are almost barrierless. This intermediate then participates in attacking the electrophilic carbon in the hydrazone. Crucially, the study reveals that the overall potential energy surface is thermodynamically favorable, and the theoretical turnover frequency (TOF) value is higher in the case of Cu(I)‐TMEDA complex catalyzed pathway.

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Section: Resultsmentioning

confidence: 99%

Computational exploration of the copper(I)‐catalyzed conversion of hydrazones to dihalogenated vinyldiazene derivatives

Askerova,

Abdullayev,

Shikhaliyev

et al. 2024

J Comput Chem

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“…But none of these works comparatively studied experimentally employed oxidizing agents. Computational tools were applied previously for the understanding of reaction mechanisms [20][21][22][23][24][25][26][27]. We chose a model reaction to reduce computational time for the present mechanistic studies: Instead of macromolecular triglyceride, but-2-ene was taken as the internal double bond carrier.…”

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confidence: 99%

Computational mechanistic studies of the carbon–carbon double bond difunctionalization via epoxidation and subsequent aminolysis in vegetable oils

Abdullayev

Abbasov

Nasirov

et al. 2021

Int J of Quantum Chemistry

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The industrial importance of the C C double bond difunctionalization in vegetable oils/fatty acid chains motivates computational studies aimed at helping to improve experimental protocols. The C C double bond epoxidation is studied with hydrogen peroxide, peracetic acid (CH 3 CO 3 H), and performic acid (HCO 3 H) oxidizing agents. The epoxide ring-opening mechanism is calculated in the presence of ZnCl 2 , NiCl 2 , and FeCl 2 Lewis acidic catalysts. Computations show that H 2 O 2 (ΔG ‡ = 39 kcal/mol, TS1 HP) is not an effective oxidizing agent compared to CH 3 CO 3 H (ΔG ‡ = 29.8 kcal/ mol, TS1 PA) and HCO 3 H (ΔG ‡ = 26.7 kcal/mol, TS1 PF). The FeCl 2 (ΔG ‡ = 14.7 kcal/ mol, TS1 FC) coordination to the epoxide oxygen facilitates the ring-opening via lower energy barriers compared to the ZnCl 2 (ΔG ‡ = 19.5 kcal/mol, TS1 ZC) and NiCl 2 (ΔG ‡ = 29.4 kcal/mol, TS1 NC) coordination. ZnCl 2 was frequently utilized as a catalyst in laboratory-scale procedures. The energetic span model identifies the FeCl 2 (FC) catalytic cycle as the best option for the epoxide ring-opening.

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Synthesis, characterization and biological evaluation of N‐substituted triazinane‐2‐thiones and theoretical–experimental mechanism of condensation reaction

Sujayev

Taslimi

Kaya

et al. 2019

Applied Organom Chemis

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The synthesis of triazinthions and their reactions with some nucleophilic reagents have been investigated during this scientific study. Thus, thiourea with a single component has been synthesized as a result of concomitant reactions of aldehyde and amines trials. The structure of the synthesized compounds was confirmed by 1H, 13C NMR spectroscopy methods. The inhibitory effects of novel N‐substituted triazinane‐2‐thione derivatives on acetylcholinesterase (AChE) activity were performed according to the spectrophotometric method of Ellman et al. These novel N‐substituted triazinane‐2‐thiones derivatives were effective inhibitors of the α‐glycosidase, cytosolic carbonic anhydrase I and II isoforms (hCA I and II), and Acetylcholinesterase (AChE) enzymes with Ki values in the range of 1.01 ± 0.28 to 2.12 ± 0.37 nm for α‐glycosidase, 13.44 ± 4.39 to 74.98 ± 6.25 nm for hCA I, 10.41 ± 4.8 to 72.6 ± 17.66 nm for hCA II, 36.82 ± 9.95 to 108.48 ± 1.17 nm for AChE, and 624.62 ± 100.34 to 1124.16 ± 205.14 nm for α‐glycosidase, respectively.

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Computational investigation of catalytic effects of CX3COOH (X = F,Cl,H) on the three-component cyclocondensation reaction

Cited by 7 publications

References 30 publications

Computational exploration of the copper(I)‐catalyzed conversion of hydrazones to dihalogenated vinyldiazene derivatives

Computational exploration of the copper(I)‐catalyzed conversion of hydrazones to dihalogenated vinyldiazene derivatives

Computational mechanistic studies of the carbon–carbon double bond difunctionalization via epoxidation and subsequent aminolysis in vegetable oils

Synthesis, characterization and biological evaluation of N‐substituted triazinane‐2‐thiones and theoretical–experimental mechanism of condensation reaction

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