1,3-Dipolar Cycloadditions by a Unified Perspective Based on Conceptual and Thermodynamics Models of Chemical Reactivity

Barrales-Martínez, César; Martínez-Araya, Jorge Ignacio; Jaque, Pablo

doi:10.1021/acs.jpca.0c10013

Cited by 11 publications

(7 citation statements)

References 104 publications

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“…Density functional theory (DFT) has successfully explained the theoretical background of molecular properties and chemical concepts [ 36 , 37 ]. In this context, we determined descriptors to analyze chemical reactivity and site selectivity of SB-1 and SB-2.…”

Section: Resultsmentioning

confidence: 99%

Physicochemical and Theoretical Characterization of a New Small Non-Metal Schiff Base with a Differential Antimicrobial Effect against Gram-Positive Bacteria

Gacitúa

Carreño

Morales-Guevara

et al. 2022

IJMS

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Searching for adequate and effective compounds displaying antimicrobial activities, especially against Gram-positive bacteria, is an important research area due to the high hospitalization and mortality rates of these bacterial infections in both the human and veterinary fields. In this work, we explored (E)-4-amino-3-((3,5-di-tert-butyl-2-hydroxybenzylidene)amino) benzoic acid (SB-1, harboring an intramolecular hydrogen bond) and (E)-2-((4-nitrobenzilidene)amino)aniline (SB-2), two Schiff bases derivatives. Results demonstrated that SB-1 showed an antibacterial activity determined by the minimal inhibitory concentration (MIC) against Staphylococcus aureus, Enterococcus faecalis, and Bacillus cereus (Gram-positive bacteria involved in human and animal diseases such as skin infections, pneumonia, diarrheal syndrome, and urinary tract infections, among others), which was similar to that shown by the classical antibiotic chloramphenicol. By contrast, this compound showed no effect against Gram-negative bacteria (Klebsiella pneumoniae, Escherichia coli, and Salmonella enterica). Furthermore, we provide a comprehensive physicochemical and theoretical characterization of SB-1 (as well as several analyses for SB-2), including elemental analysis, ESMS, 1H and 13C NMR (assigned by 1D and 2D techniques), DEPT, UV-Vis, FTIR, and cyclic voltammetry. We also performed a computational study through the DFT theory level, including geometry optimization, TD-DFT, NBO, and global and local reactivity analyses.

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Section: Resultsmentioning

confidence: 99%

Physicochemical and Theoretical Characterization of a New Small Non-Metal Schiff Base with a Differential Antimicrobial Effect against Gram-Positive Bacteria

Gacitúa

Carreño

Morales-Guevara

et al. 2022

IJMS

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“…The “similarity” condition was instead found in the synchronicity degree, unveiled by the fine structure of κ ( ξ ) along the transition regions, indicating that the set of 13DCs proceeds by a synchronous concerted mechanism. 41 In the current study, a much larger set of 13DCs between N-centred allyl-dipole with monosubstituted ethylenes (see Scheme 1) is explored, encompassing a wide range of substituents, going from mesomeric electron-donating groups (EDG), to halogens, electron-withdrawing (EWG) and strong mesomeric electron-withdrawing (sEWG), in which a Lewis acid is used as a catalyst. Thus, the substituent effect is analysed in terms of the synchronicity degree to thereby gain a deeper understanding of its role in fulfilling BEP-like trends and/or deviations.…”

Section: Resultsmentioning

confidence: 99%

“…All calculations were performed with the hybrid-GGA density functional B3LYP 45,46 with the polarized double-z basis set 6-31G(d,p). This method was chosen based on a previous work, 41 where it was shown that B3LYP has a good performance in describing 1,3-dipolar cycloadditions taking DLPNO-CCSD(T) 47 /cc-pVTZ as a reference. The accuracy of this method is enough for our purposes.…”

Section: Methodsmentioning

confidence: 99%

“…Its fine structure along the transition region has been proposed as a suitable indicator of the (a)synchronicity degree in bond breaking/ forming processes in multibond reactions. [16][17][18][19][20][21][22]41 If k(x) presents a single minimum, the process proceeds synchronously, and if two minima are present, separated by a negative local maximum, the process instead proceeds asynchronously (red profiles in Fig. 2a and b, respectively).…”

Section: Theoretical Backgroundmentioning

confidence: 99%

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A deeper analysis of the role of synchronicity on the Bell–Evans–Polanyi plot in multibond chemical reactions: a path-dependent reaction force constant

Barrales-Martínez

Jaque

2022

Phys. Chem. Chem. Phys.

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“…The distortion/interaction (D/I), or activation strain model (ASM), − in combination with the Energy Decomposition Analysis (EDA) − method, was employed to elucidate the factors controlling the DA reactivity of 4a , 4b , 1a , and 1b with 2 . This methodology was chosen because it has been used to investigate diverse cycloaddition reactions, − including cases of allenes and other cumulenes, − and has been helpful for understanding reactivity trends.…”

Section: Introductionmentioning

confidence: 99%

Diels–Alder Reactivity of Allenylboronic Acid Pinacol Ester and Related Dienophiles: Mechanistic Studies and Distortion/Interaction-Activation Strain Model Analysis

Labadie

Pellegrinet

2022

J. Org. Chem.

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A DFT study of the Diels−Alder reactions of vinylboronic acid pinacol ester, allenylboronic acid pinacol ester, methyl acrylate, and methyl 2,3-butadienoate with cyclopentadiene has been performed. Competitive mechanisms for the reactions of the carboxylic esters have been fully investigated, and similar results to those previously found for the organoboron compounds were obtained. Moreover, reactivity and selectivity patterns were correctly reproduced. The distortion/interaction-activation strain energy model analysis provided a rationale to explain the experimental outcome of the studied [4 + 2] cycloadditions. While the regioselectivity of the allenyl compounds and the relative reactivity of the boronic and carboxylic esters appear to originate from electronic effects that arise from orbital overlap and correlate with the energies of the vacant orbitals of the dienophiles, the lower reactivity of the allenes relative to the vinyl compounds may be due to the distortion of the dienophiles.

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1,3-Dipolar Cycloadditions by a Unified Perspective Based on Conceptual and Thermodynamics Models of Chemical Reactivity

Cited by 11 publications

References 104 publications

Physicochemical and Theoretical Characterization of a New Small Non-Metal Schiff Base with a Differential Antimicrobial Effect against Gram-Positive Bacteria

Physicochemical and Theoretical Characterization of a New Small Non-Metal Schiff Base with a Differential Antimicrobial Effect against Gram-Positive Bacteria

A deeper analysis of the role of synchronicity on the Bell–Evans–Polanyi plot in multibond chemical reactions: a path-dependent reaction force constant

Diels–Alder Reactivity of Allenylboronic Acid Pinacol Ester and Related Dienophiles: Mechanistic Studies and Distortion/Interaction-Activation Strain Model Analysis

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