Understanding the Polar Character Trend in a Series of Diels-Alder Reactions Using Molecular Quantum Similarity and Chemical Reactivity Descriptors

In molecular similarity there is a premise “similar molecules tend to behave similarly”; however in the actual quantum similarity field there is no clear methodology to describe the similarity in chemical reactivity, and with this end an analysis of charge-transfer (CT) processes in a series of Diels-Alder (DA) reactions between cyclopentadiene (Cp) and cyano substitutions on ethylene has been studied. The CT analysis is performed in the reagent assuming a grand canonical ensemble and the considerations for an electrophilic system using B3LYP/6-31G(d) and M06-2X/6-311 + G(d,p) methods. An analysis for CT was performed in agreement with the experimental results with a good statistical correlation (R2=0.9118) relating the polar character to the bond force constants in DA reactions. The quantum distortion analysis on the transition states (TS) was performed using molecular quantum similarity indexes of overlap and coulomb showing good correlation (R2=0.8330) between the rate constants and quantum similarity indexes. In this sense, an electronic reorganization based on molecular polarization in terms of CT is proposed; therefore, new interpretations on the electronic systematization of the DA reactions are presented, taking into account that today such electronic systematization is an open problem in organic physical chemistry. Additionally, one way to quantify the similarity in chemical reactivity was shown, taking into account the dependence of the molecular alignment on properties when their position changes; in this sense a possible way to quantify the similarity of the CT in systematic form on these DA cycloadditions was shown.

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New Insights About Aromaticity using Molecular Polarization, Molecular Quantum Similarity and Chemical Reactivity Descriptors Supported in the Density Functional Theory

Biomedical Journal of Scientific & Technical Research ◽

10.26717/bjstr.2020.25.004187 ◽

2020 ◽

Vol 25 (2) ◽

Author(s):

Alejandro Morales Bayuelo

Keyword(s):

Density Functional Theory ◽

Density Functional ◽

Chemical Reactivity ◽

Quantum Similarity ◽

Functional Theory ◽

Reactivity Descriptors ◽

The Density Functional Theory ◽

Chemical Reactivity Descriptors ◽

Molecular Quantum Similarity

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Mathematical Analysis of a Series of 4-Acetylamino-2-(3,5-dimethylpyrazol-1-yl)-6-pyridylpyrimidines: A Simple Way to Relate Quantum Similarity to Local Chemical Reactivity Using the Gaussian Orbitals Localized Theory

Journal of Theoretical Chemistry ◽

10.1155/2014/624891 ◽

2014 ◽

Vol 2014 ◽

pp. 1-13 ◽

Cited By ~ 4

Author(s):

Alejandro Morales-Bayuelo ◽

Verónica Valdiris ◽

Ricardo Vivas-Reyes

Keyword(s):

Density Functional ◽

Chemical Reactivity ◽

Point Of View ◽

Quantum Similarity ◽

Electronic Effects ◽

Fukui Functions ◽

Reactivity Descriptors ◽

Bonding Theory ◽

Molecular Quantum Similarity ◽

Gaussian Orbitals

Molecular Quantum Similarity (MQS) descriptors and Density Functional Theory (DFT) based reactivity descriptors were studied for a series of 4-Acetylamino-2-(3,5-dimethylpyrazol-1-yl)-6-pyridylpyrimidines compounds used for Parkinson’s disease (PD) treatment. The quantification of the steric and electronic effects was shown through scales of quantitative convergence; such scales allow us to establish a methodology to quantify the similarity from the local chemical reactivity (Fukui Functions) point of view. This procedure provides new considerations in the local reactivity of the A2A Adenosine receptor antagonists in a disease of difficult control as PD. In addition, we present new considerations to the localized bonding theory and show a new methodology for quantum similarity on the Fukui Functions. Considering that the Fukui functions under a condensation scheme may have ambiguities in the (DFT) context.

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Theoretical Study of the Reaction of Formation of Some Free Phosphines by Stereoselective Hydrophosphination through DFT Method

Asian Journal of Applied Chemistry Research ◽

10.9734/ajacr/2018/v1i29638 ◽

2018 ◽

pp. 1-10

Author(s):

Kouadio Valery Bohoussou ◽

Anoubilé Bénié ◽

Mamadou Guy-Richard Koné ◽

N’guessan Yao Silvère Diki ◽

Kafoumba Bamba ◽

...

Keyword(s):

Theoretical Study ◽

Chemical Reactivity ◽

Dft Method ◽

Trans Form ◽

Dft Methods ◽

Activation Barriers ◽

Reactivity Descriptors ◽

Chemical Reactivity Descriptors ◽

Theoretical Results ◽

Cis Isomer

In this work the formation of vinylphosphines was studied through the hydrophosphination reaction. The study aims to rationalize the stereoselectivity of these compounds using quantum DFT methods. This theoretical study of chemical reactivity was conducted at B3LYP/6-311 + G (d, p) level. Global chemical reactivity descriptors, stationary point energies and activation barriers were examined to foretell the relative stability of the stereoisomers formed. The various results obtained have revealed that the addition of arylphosphine to dihalogenoacetylene is stereospecific. The Trans form of vinylphosphines is more stable than the Cis form, when the substituent on phosphorus generates less or no π-conjugations. On the other hand, the Cis isomer is predominant when the aryl radical favors more π-conjugations. The theoretical results obtained are in agreement with the experimental results.

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Chemical Reactivity Descriptors for Ambiphilic Reagents: Dual Descriptor, Local Hypersoftness, and Electrostatic Potential

The Journal of Physical Chemistry A ◽

10.1021/jp902792n ◽

2009 ◽

Vol 113 (30) ◽

pp. 8660-8667 ◽

Cited By ~ 120

Author(s):

Carlos Cárdenas ◽

Nataly Rabi ◽

Paul W. Ayers ◽

Christophe Morell ◽

Paula Jaramillo ◽

...

Keyword(s):

Electrostatic Potential ◽

Chemical Reactivity ◽

Dual Descriptor ◽

Reactivity Descriptors ◽

Chemical Reactivity Descriptors

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Theoretical study of the chemical reactivity and molecular quantum similarity in a series of derivatives of 2-adamantyl-thiazolidine-4-one using density functional theory and the topo-geometrical superposition approach

International Journal of Quantum Chemistry ◽

10.1002/qua.23288 ◽

2011 ◽

Vol 112 (14) ◽

pp. 2681-2687 ◽

Cited By ~ 7

Author(s):

Alejandro Morales-Bayuelo ◽

Rosa Baldiris ◽

Juan Torres ◽

Juan E. Torres ◽

Ricardo Vivas-Reyes

Keyword(s):

Density Functional Theory ◽

Density Functional ◽

Theoretical Study ◽

Chemical Reactivity ◽

Quantum Similarity ◽

Functional Theory ◽

Molecular Quantum Similarity ◽

Derivatives Of

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New molecular target insights about protein kinases of the Plasmodium falciparum. Using molecular docking and DFT-based reactivity descriptors

Journal of Theoretical and Computational Chemistry ◽

10.1142/s0219633617500766 ◽

2017 ◽

Vol 16 (08) ◽

pp. 1750076 ◽

Cited By ~ 1

Author(s):

Alejandro Morales-Bayuelo

Keyword(s):

Plasmodium Falciparum ◽

Protein Kinases ◽

Density Functional ◽

Chemical Potential ◽

Chemical Reactivity ◽

Binding Pocket ◽

Fukui Functions ◽

Reactivity Descriptors ◽

Chemical Reactivity Descriptors ◽

Hinge Zone

Currently, there is increasing interest in the potential of malaria inhibitors in Plasmodium falciparum activity. In this work, is propose a possible alternative to classifying 154 antimalarials, with P. falciparum activity. These antimalarials were synthesized by the Chibale’s group ( http://www.kellychibaleresearch.uct.ac.za/ ), with the goal of finding new insights on the binding pocket of the protein kinase PfPK5, PfPK7, PfCDPK1, PfCDPK4, PfMAP1, and PfPK6 of the malaria parasite. However, there is only information about crystallography of PfPK5 and PfPK7. The protein kinases PfCDPK1, PfCDPK4, PfMAP1, and PfPK6 were modeled using molecular homology. The validation used shows that our homology models can be an alternative for the protein kinases from P. falciparum, unknown today. The antimalarials were classified by taking into account the interactions in the hinge zone. These ligands bind to the kinase through the formation of one of two hydrogen bonds, with the backbone residues of the hinge region connecting the kinase N- and C-terminal loops. These interactions were supported by a reactivity chemistry analysis, using global chemical reactivity descriptors such as chemical potential, hardness, softness, electrophilicity, and the Fukui functions as local reactivity descriptors, within the Density Functional Theory (DFT) context.

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Computational Nutraceutics: Chemical Reactivity Properties of the Flavonoid Naringin by Means of Conceptual DFT

Journal of Chemistry ◽

10.1155/2013/850297 ◽

2013 ◽

Vol 2013 ◽

pp. 1-8 ◽

Cited By ~ 12

Author(s):

Jorge Ignacio Martínez-Araya ◽

Guillermo Salgado-Morán ◽

Daniel Glossman-Mitnik

Keyword(s):

Active Sites ◽

Chemical Reactivity ◽

Fukui Function ◽

Conceptual Dft ◽

Density Functionals ◽

Structure And Properties ◽

Dual Descriptor ◽

Reactivity Descriptors ◽

Koopmans Theorem ◽

Chemical Reactivity Descriptors

The M06 family of density functionals has been assessed for the calculation of the molecular structure and properties of the Naringin molecule. The chemical reactivity descriptors have been calculated through Conceptual DFT. The active sites for nucleophilic and electrophilic attacks have been chosen by relating them to the Fukui function indices and the dual descriptorf(2)(r). A comparison between the descriptors calculated through vertical energy values and those arising from the Koopmans' theorem approximation has been performed in order to check for the validity of the last procedure.

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Chemical Reactivity Properties, Solubilities, and Bioactivity Scores of Some Pigments Derived from Carotenoids of Marine Origin through Conceptual DFT Descriptors

Journal of Chemistry ◽

10.1155/2019/9624108 ◽

2019 ◽

Vol 2019 ◽

pp. 1-12

Author(s):

Norma Flores-Holguín ◽

Juan Frau ◽

Daniel Glossman-Mitnik

Keyword(s):

Density Functional ◽

Chemical Reactivity ◽

Basis Set ◽

Carotenoid Pigments ◽

Density Functionals ◽

Solvation Model ◽

Conceptual Density Functional Theory ◽

Functional Theory ◽

Reactivity Descriptors ◽

Chemical Reactivity Descriptors

Five density functionals, CAM-B3LYP, LC-ωHPBE, MN12SX, N12SX, and ωB97XD, in connection with the Def2TZVP basis set were assessed together with the SMD solvation model for the calculation of the molecular properties, chemical reactivities, and solubilities of some pigments derived from astaxanthin, β-cryptoxanthin, fucoxanthin, myxol, siphonaxanthin, siphonein, and zeaxanthin marine carotenoids in the presence of different solvents (hexane, methanol, ethanol, and water). All the chemical reactivity descriptors for the systems were calculated via conceptual density functional theory (CDFT). Finally, the potential bioavailability and druggability as well as the bioactivity scores for the marine carotenoid pigments were predicted through different methodologies already reported in the literature, which have been previously validated during the study of other natural products obtained from marine sources.

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Topological Model on the Inductive Effect in Alkyl Halides Using Local Quantum Similarity and Reactivity Descriptors in the Density Functional Theory

Journal of Quantum Chemistry ◽

10.1155/2014/850163 ◽

2014 ◽

Vol 2014 ◽

pp. 1-12 ◽

Cited By ~ 3

Author(s):

Alejandro Morales-Bayuelo ◽

Ricardo Vivas-Reyes

Keyword(s):

Density Functional ◽

Chemical Potential ◽

Inductive Effect ◽

Chemical Reactivity ◽

Topological Analysis ◽

Basis Set ◽

Organic Chemical ◽

Quantum Similarity ◽

Local Exchange ◽

Reactivity Descriptors

We present a topological analysis to the inductive effect through steric and electrostatic scales of quantitative convergence. Using the molecular similarity field based in the local guantum similarity (LQS) with the Topo-Geometrical Superposition Algorithm (TGSA) alignment method and the chemical reactivity in the density function theory (DFT) context, all calculations were carried out with Amsterdam Density Functional (ADF) code, using the gradient generalized approximation (GGA) and local exchange correlations PW91, in order to characterize the electronic effect by atomic size in the halogens group using a standard Slater-type-orbital basis set. In addition, in this study we introduced news molecular bonding relationships in the inductive effect and the nature of the polar character in the C–H bond taking into account the global and local reactivity descriptors such as chemical potential, hardness, electrophilicity, and Fukui functions, respectively. These descriptors are used to find new alternative considerations on the inductive effect, unlike to the binding energy and dipole moment performed in the traditional organic chemical.

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