Unveiling the high reactivity of experimental pseudodiradical azomethine ylides within molecular electron density theory

Ríos‐Gutiérrez, Mar; Domingo, Luís R.; Jasiński, Radomir

doi:10.1039/d2cp05032c

Cited by 10 publications

(11 citation statements)

References 53 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…4). The TS, which showed a GEDT = 0.17 e, was found 11.4 kcal•mol -1 below the separated reagents [48].…”

Section: The Molecular Electron Density Theory (Medt)mentioning

confidence: 91%

A Useful Classification of Organic Reactions Based on the Flux of the Electron Density

Doming¹,

Ríos‐Gutiérrez²

2023

Sci. Rad

View full text Add to dashboard Cite

A useful classification of polar organic reactions in Forward Electron Density Flux (FEDF) and Reverse Electron Density Flux (REDF), based on the unambiguously analysis of the direction of the flux of the global electron density transfer (GEDT) at the transition state structures (TSs), has been recently proposed (RSC Adv. 2020, 10, 15394) within the Molecular Electron Density Theory. Further, non-polar reactions have been classified as Null Electron Density Flux (NEDF) (Eur. J. Org. Chem. 2020, 5938). This classification allows characterizing the nucleophilic/electrophilic species participating in polar reactions. Analysis of the electronic chemical potential m, and the electrophilicity w and nucleophilicity N indices, defined within Conceptual DFT, at the ground state (GS) of the reagents also permits to establish this classification of polar reactions.

show abstract

“…4). The TS, which showed a GEDT = 0.17 e, was found 11.4 kcal•mol -1 below the separated reagents [48].…”

Section: The Molecular Electron Density Theory (Medt)mentioning

confidence: 91%

A Useful Classification of Organic Reactions Based on the Flux of the Electron Density

Doming¹,

Ríos‐Gutiérrez²

2023

Sci. Rad

View full text Add to dashboard Cite

show abstract

“…It is important because the latest discoveries in the research of the cycloaddition reaction mechanism fully undermined the definition of the "concerted" 32CA mechanism [8,9] with the "pericyclic" reorganization of electron density within the transition state. At this moment, it is evident that within the course of the cycloaddition process, many stages with different types of electron flux are possible [10,11]. The full description of the electron reorganization requires a detailed Molecular Electron Density Theory (MEDT) study based on Electron Localization Function (ELF) techniques.…”

Section: Resultsmentioning

confidence: 99%

Full Regio- and Stereoselective Protocol for the Synthesis of New Nicotinoids via Cycloaddition Processes with the Participation of Trans-Substituted Nitroethenes: Comprehensive Experimental and MEDT Study

et al. 2023

Self Cite

View full text Add to dashboard Cite

[3 + 2] Cycloaddition reactions with the participation of Z-C-(3-pyridyl)-N-methylnitrone and series of E-2-R-nitroethenes were both experimentally and theoretically explored in the framework of Molecular Electron Density Theory. It was found that all considered processes are realized under mild conditions and in full regio- and stereocontrol. The ELF analysis additionally showed that the studied reaction proceeds by a two-stage, one-step mechanism.

show abstract

“…Using the aforementioned CDFT software tool, the Nucleophilicity N of the considered cyclopeptides was estimated and the obtained values are also presented in Table 2. According to a proposed scale for the Nucleophilicity N, [72] Kahalalides A, D and E may be considered as strong nucleophiles, while the B, C and F species should be regarded as moderate ones. Applying the same ideas as before, the local reactivity descriptors known as Fukui functions are defined as shown in Eqs.…”

Section: Resultsmentioning

confidence: 99%

Investigating the Chemical Reactivity of Kahalalides: A Promising Source of Therapeutic Peptides from Marine Natural Products Using Conceptual Density Functional Theory

Flores‐Holguín,

Frau,

Glossman‐Mitnik

2023

ChemistrySelect

View full text Add to dashboard Cite

Marine organisms have been found to produce compounds that have the potential to serve as templates for novel therapeutics. Among these compounds, peptides are of particular interest due to their intermediate size between amino acids and proteins. Kahalalides are a family of structurally complex cyclic peptides with potent cytotoxic and antitumor activities, making them promising candidates for cancer therapy. In this study, we investigate the chemical reactivity of Kahalalides A–F using Conceptual Density Functional Theory to gain insight into their bioactivity from a molecular perspective. Our investigation includes characterizing and isolating the peptides, determining their local and global properties and predicting the active reaction sites. We also calculate Bioactivity Scores to predict their biological targets. Overall, this study contributes to the discovery of new therapeutic peptides from natural sources by providing insights into their chemical reactivity and potential biological targets.

show abstract

Unveiling the high reactivity of experimental pseudodiradical azomethine ylides within molecular electron density theory

Abstract: The 32CA reactions of N-methyl azomethine ylide (AY) with styrene, benzaldehyde and methyl 2-formyl-benzoate (MFB) have been studied within Molecular Electron Density Theory (MEDT), at the ωB97X-D/6-311G(d) computational level, in...

Cited by 10 publications

References 53 publications

A Useful Classification of Organic Reactions Based on the Flux of the Electron Density

A Useful Classification of Organic Reactions Based on the Flux of the Electron Density

Full Regio- and Stereoselective Protocol for the Synthesis of New Nicotinoids via Cycloaddition Processes with the Participation of Trans-Substituted Nitroethenes: Comprehensive Experimental and MEDT Study

Investigating the Chemical Reactivity of Kahalalides: A Promising Source of Therapeutic Peptides from Marine Natural Products Using Conceptual Density Functional Theory

Contact Info

Product

Resources

About