A Mechanism Study and an Investigation of the Reason for the Stereoselectivity in the [4+2] Cycloaddition Reaction between Cyclopentadiene and Gem-substituted Ethylene Electrophiles

Aitouna, Abdelhak Ouled; Barhoumi, Ali; Zeroual, Abdellah

doi:10.58332/scirad2023v2i3a01

Cited by 12 publications

(2 citation statements)

References 29 publications

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“…Within MCs, any new bonds are not formed (Table 3). Key interatomic distances of N3-C4 and C5-N1 exist beyond the area of the range typical for new C-N bonds within transition states [47][48][49]. These types of MCs were experimentally observed earlier regarding 32CAs of ozone with ethene and ethyne [50,51].…”

Section: Resultsmentioning

confidence: 52%

On the Question of Zwitterionic Intermediates in the [3+2] Cycloaddition Reactions between Aryl Azides and Ethyl Propiolate

Dresler,

Woliński,

Wróblewska

et al. 2023

Molecules

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The molecular mechanism of the [3+2] cycloaddition reactions between aryl azides and ethyl propiolate was evaluated in the framework of the Molecular Electron Density Theory. It was found that independently of the nature of the substituent within the azide molecule, the cycloaddition process is realized via a polar but single-step mechanism. All attempts of localization as postulated earlier by Abu-Orabi and coworkers’ zwitterionic intermediates were not successful. At the same time, the formation of zwitterions with an “extended” conformation is possible on parallel reaction paths. The ELF analysis shows that the studied cycloaddition reaction leading to the 1,4-triazole proceeds by a two-stage one-step mechanism. It also revealed that both zwitterions are created by the donation of the nitrogen atom’s nonbonding electron densities to carbon atoms of ethyl propiolate.

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Section: Resultsmentioning

confidence: 52%

On the Question of Zwitterionic Intermediates in the [3+2] Cycloaddition Reactions between Aryl Azides and Ethyl Propiolate

Dresler,

Woliński,

Wróblewska

et al. 2023

Molecules

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show abstract

“…Analysis of the electronic properties of organic molecules is an important and universal tool for predicting their reactivity [67][68][69]. This approach was recently and successfully applied to interpret the reactivity of different types of molecular segments and the course of many bimolecular organic processes [70][71][72][73][74].…”

Section: Power Of the Global And Local Interactions In The Context Of...mentioning

confidence: 99%

Energetic Aspects and Molecular Mechanism of 3-Nitro-substituted 2-Isoxazolines Formation via Nitrile N-Oxide [3+2] Cycloaddition: An MEDT Computational Study

Dresler,

Wróblewska,

Jasiński

2024

Molecules

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Regioselectivity and the molecular mechanism of the [3+2] cycloaddition reaction between nitro-substituted formonitrile N-oxide 1 and electron-rich alkenes were explored on the basis of the wb97xd/6-311+G(d) (PCM) quantum chemical calculations. It was established that the thermodynamic factors allow for the formation of stable cycloadducts along all considered models. The analysis of the kinetic parameters of the main processes show that all [3+2] cycloadditions should be realized with full regioselectivity. In all cases, the formation of 5-substituted 3-nitro-2-isoxazolidines is clearly preferred. It is interesting that regiodirection is not determined by the local electrophile/nucleophile interactions but by steric effects. From a mechanistic point of view, all considered reactions should be treated as polar, one-step reactions. All attempts to locate the hypothetical zwitterionic intermediates along the cycloaddition paths were, however, not successful.

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Molecular docking, expounding the chemo-, regio-selectivity, and the mechanism of [3 + 2] cycloloaddition reaction between nitrile-imine and (thio)-chalcone

Ryachi,

idrissi,

Mohammad-Salim

et al. 2024

Monatsh Chem

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A Mechanism Study and an Investigation of the Reason for the Stereoselectivity in the [4+2] Cycloaddition Reaction between Cyclopentadiene and Gem-substituted Ethylene Electrophiles

Cited by 12 publications

References 29 publications

On the Question of Zwitterionic Intermediates in the [3+2] Cycloaddition Reactions between Aryl Azides and Ethyl Propiolate

On the Question of Zwitterionic Intermediates in the [3+2] Cycloaddition Reactions between Aryl Azides and Ethyl Propiolate

Energetic Aspects and Molecular Mechanism of 3-Nitro-substituted 2-Isoxazolines Formation via Nitrile N-Oxide [3+2] Cycloaddition: An MEDT Computational Study

Molecular docking, expounding the chemo-, regio-selectivity, and the mechanism of [3 + 2] cycloloaddition reaction between nitrile-imine and (thio)-chalcone

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