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

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)....

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Autores principales:	Karolina Zawadzińska, Mar Ríos-Gutiérrez, Karolina Kula, Przemysław Woliński, Barbara Mirosław, Tomasz Krawczyk, Radomir Jasiński
Formato:	article
Lenguaje:	EN
Publicado:	MDPI AG 2021
Materias:	[3 + 2] cycloaddition nitrile oxides nitroalkenes reactivity molecular mechanism molecular electron density theory Organic chemistry QD241-441
Acceso en línea:	https://doaj.org/article/a725887f007044daa52102867672fa74
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spelling	oai:doaj.org-article:a725887f007044daa52102867672fa742021-11-25T18:27:09ZThe Participation of 3,3,3-Trichloro-1-nitroprop-1-ene in the [3 + 2] Cycloaddition Reaction with Selected Nitrile <i>N</i>-Oxides in the Light of the Experimental and MEDT Quantum Chemical Study10.3390/molecules262267741420-3049https://doaj.org/article/a725887f007044daa52102867672fa742021-11-01T00:00:00Zhttps://www.mdpi.com/1420-3049/26/22/6774https://doaj.org/toc/1420-3049The regioselective <i>zw-type</i> [3 + 2] cycloaddition (32CA) reactions of a series of aryl-substituted nitrile <i>N</i>-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<sup>−1</sup> and an exergonic character of 28.4 kcal·mol<sup>−1</sup> 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-CCCl<sub>3</sub> interaction, these reactions follow a two-stage one-step mechanism in which formation of the O-C(CCl<sub>3</sub>) bond takes place once the C-C(NO<sub>2</sub>) 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.Karolina ZawadzińskaMar Ríos-GutiérrezKarolina KulaPrzemysław WolińskiBarbara MirosławTomasz KrawczykRadomir JasińskiMDPI AGarticle[3 + 2] cycloadditionnitrile oxidesnitroalkenesreactivitymolecular mechanismmolecular electron density theoryOrganic chemistryQD241-441ENMolecules, Vol 26, Iss 6774, p 6774 (2021)
institution	DOAJ
collection	DOAJ
language	EN
topic	[3 + 2] cycloaddition nitrile oxides nitroalkenes reactivity molecular mechanism molecular electron density theory Organic chemistry QD241-441
spellingShingle	[3 + 2] cycloaddition nitrile oxides nitroalkenes reactivity molecular mechanism molecular electron density theory Organic chemistry QD241-441 Karolina Zawadzińska Mar Ríos-Gutiérrez Karolina Kula Przemysław Woliński Barbara Mirosław Tomasz Krawczyk Radomir Jasiński The Participation of 3,3,3-Trichloro-1-nitroprop-1-ene in the [3 + 2] Cycloaddition Reaction with Selected Nitrile <i>N</i>-Oxides in the Light of the Experimental and MEDT Quantum Chemical Study
description	The regioselective <i>zw-type</i> [3 + 2] cycloaddition (32CA) reactions of a series of aryl-substituted nitrile <i>N</i>-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<sup>−1</sup> and an exergonic character of 28.4 kcal·mol<sup>−1</sup> 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-CCCl<sub>3</sub> interaction, these reactions follow a two-stage one-step mechanism in which formation of the O-C(CCl<sub>3</sub>) bond takes place once the C-C(NO<sub>2</sub>) 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.
format	article
author	Karolina Zawadzińska Mar Ríos-Gutiérrez Karolina Kula Przemysław Woliński Barbara Mirosław Tomasz Krawczyk Radomir Jasiński
author_facet	Karolina Zawadzińska Mar Ríos-Gutiérrez Karolina Kula Przemysław Woliński Barbara Mirosław Tomasz Krawczyk Radomir Jasiński
author_sort	Karolina Zawadzińska
title	The Participation of 3,3,3-Trichloro-1-nitroprop-1-ene in the [3 + 2] Cycloaddition Reaction with Selected Nitrile <i>N</i>-Oxides in the Light of the Experimental and MEDT Quantum Chemical Study
title_short	The Participation of 3,3,3-Trichloro-1-nitroprop-1-ene in the [3 + 2] Cycloaddition Reaction with Selected Nitrile <i>N</i>-Oxides in the Light of the Experimental and MEDT Quantum Chemical Study
title_full	The Participation of 3,3,3-Trichloro-1-nitroprop-1-ene in the [3 + 2] Cycloaddition Reaction with Selected Nitrile <i>N</i>-Oxides in the Light of the Experimental and MEDT Quantum Chemical Study
title_fullStr	The Participation of 3,3,3-Trichloro-1-nitroprop-1-ene in the [3 + 2] Cycloaddition Reaction with Selected Nitrile <i>N</i>-Oxides in the Light of the Experimental and MEDT Quantum Chemical Study
title_full_unstemmed	The Participation of 3,3,3-Trichloro-1-nitroprop-1-ene in the [3 + 2] Cycloaddition Reaction with Selected Nitrile <i>N</i>-Oxides in the Light of the Experimental and MEDT Quantum Chemical Study
title_sort	participation of 3,3,3-trichloro-1-nitroprop-1-ene in the [3 + 2] cycloaddition reaction with selected nitrile <i>n</i>-oxides in the light of the experimental and medt quantum chemical study
publisher	MDPI AG
publishDate	2021
url	https://doaj.org/article/a725887f007044daa52102867672fa74
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The Participation of 3,3,3-Trichloro-1-nitroprop-1-ene in the [3 + 2] Cycloaddition Reaction with Selected Nitrile <i>N</i>-Oxides in the Light of the Experimental and MEDT Quantum Chemical Study

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