Experimental and theoretical studies on polar Diels–Alder reactions of 1-nitronaphathalene developed in ionic liquids

Mancini, Paolo; Rosa, Claudia Della; Ormachea, Carla; Kneeteman, Marı́a N.; Domingo, Luís R.

doi:10.1039/c3ra42042f

Cited by 10 publications

(7 citation statements)

References 70 publications

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“…[36] For example, Diels-Alder reactions involving nitroaromatic compounds such as nitronaphthalene, nitroindoles and nitropyrroles have been extensively studied by the groups of Domingo and Mancini. [37][38][39] Finally, B3 reaction involves the classical Diels-Alder between furan and maleic anhydride to form norcantharidin, whose endo/exo diastereoselectivity under kinetic/thermodynamic control has been debated over years. [40][41][42][43][44] Recently, Houk and co-workers have studied computationally a class of Diels-Alder reactions in which the dienophile has a cyclic allene structure.…”

Section: Introductionmentioning

confidence: 99%

Efficient and Accurate Description of Diels‐Alder Reactions Using Density Functional Theory**

et al. 2022

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Modeling chemical reactions using Quantum Chemistry is a widely used predictive strategy capable to complement experiments in order to understand the intrinsic mechanisms guiding the chemicals towards the most favorable reaction products. However, at this purpose, it is mandatory to use reliable and computationally tractable theoretical methods. In this work, we focus on six Diels-Alder reactions of increasing complexity and perform an extensive benchmark of middle-to low-cost computational approaches to predict the characteristic reactions energy barriers.We found that Density Functional Theory, using the ωB97XD, LC-ωPBE, CAMÀ B3LYP, M11 and MN12SX functionals, with empirical dispersion corrections coupled to an affordable 6-31G basis set, provides quality results for this class of reactions, at a small computational effort. Such efficient and reliable simulation protocol opens perspectives for hybrid QM/MM molecular dynamics simulations of Diels-Alder reactions including explicit solvation.

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Section: Introductionmentioning

confidence: 99%

Efficient and Accurate Description of Diels‐Alder Reactions Using Density Functional Theory**

et al. 2022

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“…In order to understand the kinetic effects of the IL on the studied DA reactions, we have performed DFT calculations in the presence of the DCM organic solvent and the EPTFA IL solvent. For this purpose, we have used a simple model [30][31][32][33][34][35][36][37] www.prkm.co.uk Figure 2). Indeed, the calculated barriers, given in Tables 3b and 3c, for the para and meta channels along the two stereoselective pathways in the presence of DCM and EPTFA solvents show that the para channel is kinetically and thermodynamically more favoured than the meta channel.…”

Section: Solvent Phase Calculationsmentioning

confidence: 99%

“…Domingo et al [27] also stated that DA reactions of 1-nitronaphthalene to form phenanthrenol derivatives occur more efficiently in protic and aprotic ILs than in molecular organic solvents. The mechanisms by which IL solvents enhance the rate and selectivity of the reaction and how IL properties can affect DA reactions are discussed on the basis of several models [30][31][32][33][34][35][36][37]. For instance, Chiappe et al [33] deduced, using theoretical calculations and empirical parameters, that the primary role of the cationic component of the IL on the selectivity can be attributed to the hydrogen bonding ability and the dipolarity/polarisability of a single IL cation, or to a more coordinated effect of the solvation shell.…”

Section: Introductionmentioning

confidence: 99%

“…Hayaki et al [34] examined theoretically the DA reaction of cyclopentadiene with methyl acrylate in room temperature ILs using quantum molecular orbital theory combined with a multicomponent reference interaction site model. Mancini et al [35] evaluated the effects of the polar IL considering two computational models. In Model I, explicit effects of the PIL were considered by forming a hydrogen bond between the reagents and the polar IL while in Model II, implicit solvent effects of the PIL were considered by including electrostatic interactions modelled by the polarisable continuum model (PCM) of Tomasi's group, using a solvent which has a dielectric constant closer to an IL.…”

Section: Introductionmentioning

confidence: 99%

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Theoretical Investigation of the Kinetic Effect of the 1-Ethylpyridinium Trifluoroacetate Ionic Liquid in the Acceleration of Diels–Alder Reactions of Isoprene with Acrylic Acid and Acrylonitrile

Chemouri

Mekelleche

2017

Progress in Reaction Kinetics and Mechanism

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The mechanism, the regioselectivity, the stereoselectivity and the kinetics of Diels–Alder reactions of isoprene with acrylic acid and acrylonitrile have been studied, at the B3PW91/6-31G(d,p) level of theory, both in the gas phase and in the presence of organic [dichloromethane (DCM)] and ionic liquid [1-ethylpyridinium trifluoroacetate (EPTFA)] solvents. Intrinsic reaction coordinate calculations show that these reactions take place through an asynchronous concerted mechanism leading to the endo para cycloadducts as the major products in the gas phase and to the exo para cycloadducts as the major products both in organic and in ionic liquid solvents. The explicit solvation model involving the coordination of one molecule of the solvent with the dienophiles shows a considerable decrease of the activation energy when passing from DCM to EPTFA. The enhancement of these cycloaddition reactions can be explained by the strong hydrogen bonding created between the ion pair of the ionic liquid and the oxygen atom of the dienophile reagents. Moreover, density functional theory-based reactivity indices also show an increase of the reaction polarity and consequently of the reaction rate, when replacing DCM solvent by EPTFA solvent. The results obtained give evidence that the ionic liquid EPTFA is an excellent solvent for Diels–Alder reactions in comparison with conventional organic solvents.

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“…Δ G 1 , Δ G 2 , and Δ G 3 are the solvation energies for different solutes. This methodology of solvation free energy was widely used in other systems. , The advantage of the current model is that not only the implicit solvent effect is considered but also the interaction between solvent molecule and solute is explicitly considered. Lastly, the effects of the basis set superposition error (BSSE) on the interaction energy have also been considered.…”

Section: Computational Detailsmentioning

confidence: 99%

A DFT Study of the Extractive Desulfurization Mechanism by [BMIM]⁺[AlCl₄]⁻ Ionic Liquid

Chang

Zhu

et al. 2015

J. Phys. Chem. B

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In this work, the interaction nature between [BMIM](+)[AlCl4](-) ionic liquid (IL) and aromatic sulfur compounds (thiophene, benzothiophene, and dibenzothiophene) has been studied by means of density functional theory (M06-2X functional) combined with an implicit solvation model. Although [BMIM](+)[AlCl4](-) is a metal-containing IL, its extractive desulfurization mechanism is different from other metal-containing ILs but similar to non-metal-containing ILs. Important reactions involved in extractive desulfurization (EDS) were systematically studied. Our results have demonstrated that both the cation and the anion play important roles in EDS. On the basis of the structure analysis, reduced density gradient analaysis (RDG), and energy decomposition analysis, [BMIM](+) cation affords a π-π interaction while [AlCl4](-) anion provides a hydrogen bonding interaction. Electrostatic potential analysis implies the dominant π-π interaction and hydrogen bonding interaction are driven by electrostatic interaction between IL and aromatic sulfur compounds. Interaction energy between [BMIM](+)[AlCl4](-) and thiophene (TH), benzothiophene (BT), and dibenzothiophene (DBT) follows the order TH < BT < DBT. Moreover, Al-containing IL with a high molar ratio of AlCl3 ([BMIMCl]/2[AlCl3]) has also been studied. Results show that [Al2Cl7](-) species will be formed with excess AlCl3. However, the [Al2Cl7](-)-based IL cannot improve the EDS performance. Improvement of EDS performance with a high molar ratio of AlCl3 is credited to the Lewis acidity of AlCl3. Charge analysis reveals that there is no obvious charge transfer during the reaction, which is different from Fe-containing ILs as well as solid sorbents. In addition, CH-π interaction is not important for the current system.

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Experimental and theoretical studies on polar Diels–Alder reactions of 1-nitronaphathalene developed in ionic liquids

Cited by 10 publications

References 70 publications

Efficient and Accurate Description of Diels‐Alder Reactions Using Density Functional Theory**

Efficient and Accurate Description of Diels‐Alder Reactions Using Density Functional Theory**

Theoretical Investigation of the Kinetic Effect of the 1-Ethylpyridinium Trifluoroacetate Ionic Liquid in the Acceleration of Diels–Alder Reactions of Isoprene with Acrylic Acid and Acrylonitrile

A DFT Study of the Extractive Desulfurization Mechanism by [BMIM]⁺[AlCl₄]⁻ Ionic Liquid

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Experimental and theoretical studies on polar Diels–Alder reactions of 1-nitronaphathalene developed in ionic liquids

Cited by 10 publications

References 70 publications

Efficient and Accurate Description of Diels‐Alder Reactions Using Density Functional Theory**

Efficient and Accurate Description of Diels‐Alder Reactions Using Density Functional Theory**

Theoretical Investigation of the Kinetic Effect of the 1-Ethylpyridinium Trifluoroacetate Ionic Liquid in the Acceleration of Diels–Alder Reactions of Isoprene with Acrylic Acid and Acrylonitrile

A DFT Study of the Extractive Desulfurization Mechanism by [BMIM]+[AlCl4]− Ionic Liquid

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A DFT Study of the Extractive Desulfurization Mechanism by [BMIM]⁺[AlCl₄]⁻ Ionic Liquid