Organosilicon azoles: Structure, silylotropy and NMR spectroscopy

Ларина, Л. И.

doi:10.1016/bs.aihch.2019.08.001

Cited by 10 publications

(9 citation statements)

References 175 publications

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“…Dynamic NMR spectroscopy is widely used in organic chemistry to study dynamic processes in a molecule, for example see reference. [28][29][30] The dynamic 1 H NMR F I G U R E 3 E-and Z-isomers of compounds 1 and 6 F I G U R E 2 The natural polyamines method was used to determine values of free energy of activation (ΔG ≠ c ). Proton NMR spectra with temperature variation were recorded in DMSO-d 6 medium.…”

Section: Resultsmentioning

confidence: 99%

Acrylamide derivatives: A dynamic nuclear magnetic resonance study

Ларина

Albanov

Zelinskiy

et al. 2023

Magnetic Reson in Chemistry

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Substituted acrylamides have found an extensive application in organic and medical chemistry; therefore, it is very important to get insight into their features such as electronic structure, spectral properties, and stereochemical transformations. A correct interpretation of the chemical behavior and biological activity of these heteroatomic systems is impossible without knowledge of the structure of stereodynamic forms and factors determining their relative stability. The structure and peculiarities of stereodynamic behavior of substituted acrylamides and their model compounds were studied by dynamic and multinuclear 1H, 13C, and 15N nuclear magnetic resonance (NMR) spectroscopy in CDCl3 and DMSO‐d6 solution. It has been established that acrylamides in solution are realized as Z‐ and E‐isomers, with the E‐rotamer being somewhat predominant. The obtained experimental values of the free activation energy of rotamers vary within 15–17 kcal/mol, depending on the stereochemical structure of the molecule. 15N NMR spectroscopy is the most reliable and fastest method for determining the structural and stereochemical features of nitrogen‐containing compounds.

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Section: Resultsmentioning

confidence: 99%

Acrylamide derivatives: A dynamic nuclear magnetic resonance study

Ларина

Albanov

Zelinskiy

et al. 2023

Magnetic Reson in Chemistry

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“…The derivatives of azoles, in particular, 1,2,3-triazoles hold a special place in heterocyclic chemistry and find extensive applications in diverse fields of agriculture, materials science, chemical biology, and medicinal chemistry. Readily available 1,2,3-triazoles, with a wide range of various activities, have long been used as high-energy materials, ionic liquids, medicinal products, radiosensitizers, universal bases in peptide nucleic acids, plasticizers, dyes, plant growth regulators, pesticides and herbicides, synthons for fine organic synthesis, and precursors for nanocomposites. − 1,2,3-Triazole derivatives are successfully employed to create numerous drug scaffolds exhibiting anti-HIV, anticancer, antiviral, antibacterial, anti-inflammatory, antiproliferative, aticholinesterase, antioxidant, antifungal activity, etc. ,− ,,,− ,− The therapeutic effects of many compounds containing a 1,2,3-triazole moiety are also well-known.…”

Section: Introductionmentioning

confidence: 99%

Stereochemical and Computational NMR Survey of 1,2,3-Triazoles: in Search of the Original Tauto-Conformers

Semenov,

Larina

2024

J. Phys. Chem. A

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The conformational analysis of nine functionalized 1,2,3-triazoles was carried out by the correlation of calculated and experimental high-level nuclear magnetic resonance (NMR) chemical shifts. In solution, the studied triazoles are in exchange dynamic equilibrium caused by their prototropic tautomerism of the NH-proton. The experimentally unresolved NMR signals were assigned for most of the compounds. A more thorough survey was conducted for 4-t-butyl-1,2,3-triazole-5-carbaldehyde oxime. The analysis performed within the framework of the DP4+ formalism completely confirmed the hypothesis of the predominance of the 2H-tautomer. Thus, the methodology for estimating stereochemical structures in the absence of some experimental data allowed the most stable conformations for dynamic systems with different tautomeric ratios to be reliably identified.

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“…Our ongoing research on functionalized azoles and related compounds has been presented in a monograph on nitroazoles [ 13 ] and several reviews devoted to the chemistry of five-membered azoles and their benzannelated analogs [ 14 , 15 , 16 , 17 ], organosilicon azoles [ 18 ], NMR spectroscopy and mass-spectrometry of nitroazoles [ 19 , 20 ], and structure and electronic effects of five-membered nitrogenated heterocycles [ 21 ]. Furthermore, tautomerism and the stereochemical structure of functional azoles have been comprehensively researched [ 22 , 23 , 24 , 25 , 26 ]. The problems of prototropy of NH -unsubstituted azoles [ 23 ] and silylotropy of N -silylated analogs [ 25 , 26 ] have been discussed and analyzed in detail using the methods of multinuclear and dynamic NMR spectroscopy and quantum chemistry.…”

Section: Introductionmentioning

confidence: 99%

“…Furthermore, tautomerism and the stereochemical structure of functional azoles have been comprehensively researched [ 22 , 23 , 24 , 25 , 26 ]. The problems of prototropy of NH -unsubstituted azoles [ 23 ] and silylotropy of N -silylated analogs [ 25 , 26 ] have been discussed and analyzed in detail using the methods of multinuclear and dynamic NMR spectroscopy and quantum chemistry. The results of the study of the structural peculiarities and tautomerism of functionalized azoles in the solid state using the nuclear quadrupole resonance method [ 24 ] summarized.…”

Section: Introductionmentioning

confidence: 99%

Organophosphorus Azoles Incorporating a Tetra-, Penta-, and Hexacoordinated Phosphorus Atom: NMR Spectroscopy and Quantum Chemistry

Ларина

2023

Molecules

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The review presents extensive data (from the author’s work and the literature) on the stereochemical structure of functionalized organophosphorus azoles (pyrroles, pyrazoles, imidazoles and benzazoles) and related compounds, using multinuclear 1Н, 13С, 31Р NMR spectroscopy and quantum chemistry. 31P NMR spectroscopy, combined with high-level quantum-chemical calculations, is the most convenient and reliable approach to studying tetra-, penta-, and hexacoordinated phosphorus atoms of phosphorylated N-vinylazoles and evaluating their Z/E isomerization.

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Organosilicon azoles: Structure, silylotropy and NMR spectroscopy

Cited by 10 publications

References 175 publications

Acrylamide derivatives: A dynamic nuclear magnetic resonance study

Acrylamide derivatives: A dynamic nuclear magnetic resonance study

Stereochemical and Computational NMR Survey of 1,2,3-Triazoles: in Search of the Original Tauto-Conformers

Organophosphorus Azoles Incorporating a Tetra-, Penta-, and Hexacoordinated Phosphorus Atom: NMR Spectroscopy and Quantum Chemistry

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