Investigation into the regiochemistry of some isoxazoles derived from 1,3-dipolar cycloaddition of 4-nitrobenzonitrile oxide with some dipolarophiles: A combined theoretical and experimental studies

Dorostkar-Ahmadi, Nadieh; Bakavoli, Mehdi; Moeinpour, Farid; Davoodnia, Abolghasem

doi:10.1016/j.saa.2011.04.071

Cited by 9 publications

(3 citation statements)

References 28 publications

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“…The most common is from transition state theory to find out the mechanisms of the reaction and the most probable pathway with the lowest activation barrier. Many computational studies have been reported on the reaction between nitrones and nitrile oxides with numerous electron-rich or -deficient dipolarophiles [17][18][19][20][21][22][23][24][25][26]. To elaborate on some of the studies, Zhao et al [17] reported that the steric properties of the reactants affect heavily on the thermodynamically stable product to be formed.…”

Section: Introductionmentioning

confidence: 99%

“…Nacereddine and coworkers [18] also reported a good corroboration of their DFT methods to experimental results and found a good insight on the stabilization of secondary π orbital interaction to give a low lying transition state. However, this method is very time consuming due to the calculations on the higher order saddle points in the reaction coordinate and it is often needed to be paired with other theoretical data like bond parameters and NMR calculations to get a good conclusion as shown by Bakavoli and coworkers [19]. Solvent effects and Lewis acid behaviour of the reaction have also been investigated extensively by Domingo [24].…”

Section: Introductionmentioning

confidence: 99%

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The Theoretical Study on the Mechanism of [3+2] Cycloaddition Reactions between α,β-unsaturated Selenoaldehyde with Nitrone and with Nitrile Oxide

Mohammad‐Salim¹,

Hassan²,

Abdallah³

et al. 2020

J. Mex. Chem. Soc.

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Abstract. The reaction mechanisms of [3+2] cycloaddition (32CA) between the α,β-unsaturated selenoaldehyde with nitrone and nitrile oxide were investigated theoretically using the molecular electron density theory (MEDT). Selenoaldehyde has two unsaturations which allow for the cycloaddition occurring. It was expected to undergo four regioisomeric reaction paths in two separate reactions with nitrone and nitrile oxide. The study was conducted using ab initio approach at MP2/6-31G(d) level of theory. Potential energy surfaces were generated from the energies of the stationary points involved in the mechanisms and the dominant reaction pathways were identified. It was found that Pathway 3 and 4 are the two competing reaction channels, where the cycloaddition reaction occurs at the selenium-analogue carbonyl group of selenoaldehyde. The reactivity indices were analysed at the ground state of the reactants to predict the reactivity of studied organic molecules in 32CA reactions. Analysis of the electronic structure of nitrone and nitrile oxide, the three-atom-components (TACs), and their participation in 32CA reactions towards selenoaldehyde allows establishing a useful classification of 32CA reactions into zwitterionin-type (zw-type) reactions involving TACs with a high zwitterionic character. Resumen. Se estudia teóricamente, utilizando la teoría de la densidad electrónica molecular (MEDT), el mecanismo de reacción de la cicloadición [3+2] (32CA) entre selenoaldehídos α, β insaturados con nitrona y óxido de nitrilo. El selenoaldehído tiene dos insaturaciones que permiten la cicloadición. Se esperaba que la reacción se llevara a cabo a lo largo de cuatro caminos regioisoméricos en dos reacciones separadas con la nitrona y el óxido de nitrilo. Se realizó un estudio ab initio con el nivel de teoría MP2/6-31G(d). Se generaron superficies de energía potencial a partir de las energías de los puntos estacionarios involucrados en el mecanismo y se identificaron los caminos de reacción dominantes. Se encontró que dos rutas, la 3 y la 4, son los canales de reacción que compiten para que ocurra la cicloadición en el grupo carbonilo análogo al selenio del selenoaldheído. Se analizaron los índices de reactividad de los estados basales de los reactivos para predecir la reactividad de las moléculas orgánicas estudiadas en las reacciones 32CA. El análisis de la estructura electrónica de la nitrona y el óxido de nitrilo, de las componentes triatómicas (TACs) y de su participación en las reacciones 32CA hacia el selenoaldheído permite clasificar a las reacciones 32CA en tipo zwitteriónico (zw) que involucran a los TACs con un elevado carácter zwitteriónico.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

The Theoretical Study on the Mechanism of [3+2] Cycloaddition Reactions between α,β-unsaturated Selenoaldehyde with Nitrone and with Nitrile Oxide

Mohammad‐Salim¹,

Hassan²,

Abdallah³

et al. 2020

J. Mex. Chem. Soc.

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“…8 Experimentally; it has been found that the cycloaddition reactions of nitrilimines 1a-c with E-3-(dimethylamino)-1-(10H-phenothiazin-2-yl) prop-2-en-1-one 2 give preferentially the cycloadducts 3a, 3b and 3c respectively, shown in Scheme 1. 9 In continuation of our studies on the mechanism and regioselectivity of the1,3-DC reactions, [10][11][12][13][14][15][16][17][18] we became interested in the above mentioned reactions based on activation energy calculations, the distortion/interaction model and DFT-based reactivity indexes.…”

Section: Introductionmentioning

confidence: 99%

Theoretical analysis of the mechanism and regioselectivity of the 1, 3-dipolar cycloaddition of E-3-(dimethylamino)-1-(10H-phenothiazin-2-yl)prop-2-en-1-one with some nitrilimines using DFT and the distortion/interaction model

Moeinpour

Khojastehnezhad

2015

ACSi

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The regiochemistry of 1,3-dipolar cycloaddition reactions of E-3-(dimethylamino)-1-(10H-phenothiazin-2-yl) prop-2-en-1-one with some nitrilimines were investigated using density functional theory (DFT) -based reactivity indexes, activation energy calculations and the distortion/interaction model at B3LYP/6-311G(d,p) level of theory. Analysis of the geometries and bond orders (BOs) at the TS structures associated with the different reaction pathways shows that these 1,3-dipolar cycloaddition reactions occur via an asynchronous concerted mechanism.

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A theoretical investigation of the regio- and stereoselectivities of the [3 + 2] cycloaddition reaction between ethyl vinyl ether and substituted α-alkoxynitrones

et al. 2022

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Investigation into the regiochemistry of some isoxazoles derived from 1,3-dipolar cycloaddition of 4-nitrobenzonitrile oxide with some dipolarophiles: A combined theoretical and experimental studies

Cited by 9 publications

References 28 publications

The Theoretical Study on the Mechanism of [3+2] Cycloaddition Reactions between α,β-unsaturated Selenoaldehyde with Nitrone and with Nitrile Oxide

The Theoretical Study on the Mechanism of [3+2] Cycloaddition Reactions between α,β-unsaturated Selenoaldehyde with Nitrone and with Nitrile Oxide

Theoretical analysis of the mechanism and regioselectivity of the 1, 3-dipolar cycloaddition of E-3-(dimethylamino)-1-(10H-phenothiazin-2-yl)prop-2-en-1-one with some nitrilimines using DFT and the distortion/interaction model

A theoretical investigation of the regio- and stereoselectivities of the [3 + 2] cycloaddition reaction between ethyl vinyl ether and substituted α-alkoxynitrones

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