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The Participation of 3,3,3-Trichloro-1-nitroprop-1-ene in the [3+2] Cycloaddition Reaction with Selected Nitrile N-Oxides in the Light of the Experimental and MEDT Quantum Chemical Study

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The Participation of 3,3,3-Trichloro-1-nitroprop-1-ene in the [3+2] Cycloaddition Reaction with Selected Nitrile N-Oxides in the Light of the Experimental and MEDT Quantum Chemical Study

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dc.contributor.author	Zawadzinska, Karolina
dc.contributor.author	Ríos Gutiérrez, Mª del Mar
dc.contributor.author	Kula, Karolina
dc.contributor.author	Wolinski, Przemysław
dc.contributor.author	Mirosław, Barbara
dc.contributor.author	Krawczyk, Tomasz
dc.contributor.author	Jasiński, Radomir
dc.date.accessioned	2022-01-17T14:40:08Z
dc.date.available	2022-01-17T14:40:08Z
dc.date.issued	2021
dc.identifier.citation	Zawadzinska, Karolina Ríos Gutiérrez, Mª del Mar Kula, Karolina Wolinski, Przemys&#322aw Miros&#322aw, Barbara Krawczyk, Tomasz Jasi&#324ski, Radomir 2021 The Participation of 3,3,3-Trichloro-1-nitroprop-1-ene in the [3+2] Cycloaddition Reaction with Selected Nitrile N-Oxides in the Light of the Experimental and MEDT Quantum Chemical Study Molecules 26 6774 1 13
dc.identifier.uri	https://hdl.handle.net/10550/81342
dc.description.abstract	The regioselective zw-type [3 + 2] cycloaddition (32CA) reactions of a series of aryl-substituted nitrile N-oxides (NOs) with trichloronitropropene (TNP) have been both experimentally and theoretically studied within the Molecular Electron Density Theory (MEDT). Zwitterionic NOs behave as moderate nucleophiles while TNP acts as a very strong electrophile in these polar 32CA reactions of forward electron density flux, which present moderate activation Gibbs free energies of 22.8-25.6 kcal·mol−1 and an exergonic character of 28.4 kcal·mol−1 that makes them irreversible and kinetically controlled. The most favorable reaction is that involving the most nucleophilic MeO-substituted NO. Despite Parr functions correctly predicting the experimental regioselectivity with the most favorable O-CCCl3 interaction, these reactions follow a two-stage one-step mechanism in which formation of the O-C(CCl3) bond takes place once the C-C(NO2) bond is already formed. The present MEDT concludes that the reactivity differences in the series of NOs come from their different nucleophilic activation and polar character of the reactions, rather than any mechanistic feature.
dc.language.iso	eng
dc.relation.ispartof	Molecules, 2021, vol. 26, num. 6774, p. 1-13
dc.subject	Reaccions químiques
dc.subject	Química orgànica
dc.title	The Participation of 3,3,3-Trichloro-1-nitroprop-1-ene in the [3+2] Cycloaddition Reaction with Selected Nitrile N-Oxides in the Light of the Experimental and MEDT Quantum Chemical Study
dc.type	journal article	es_ES
dc.date.updated	2022-01-17T14:40:10Z
dc.identifier.doi	10.3390/molecules26226774
dc.identifier.idgrec	149757
dc.rights.accessRights	open access	es_ES