Elucidation of the substitutent effects on the reaction pathway of the cycloaddition of 1,3-diazabuta-1,3-dienes with ketenes using DFT-based reactivity indexes

Chemouri, Hafida; Mekelleche, Sidi Mohamed

doi:10.1016/j.theochem.2007.02.028

Cited by 12 publications

(4 citation statements)

References 31 publications

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“…19 Finally, Chemouri and Mekelleche recently reported a theoretical study dealing with the mechanism and the regiochemistry of the cycloaddition of 1,3-diazabuta-1,3-dienes with ketenes using DFT-based reactivity indexes. 34 With the aim to clarify the different outcome observed by reacting conjugated versus unconjugated ketenes, the problem was tentatively approached from a theoretical point of view. The investigation was restricted to all potential products arising from the [2+2] and [4+2] cycloaddition reaction of diazadiene 1a with alkynyl ketenes derived from 3a and 3b.…”

Section: Methodsmentioning

confidence: 99%

Cycloaddition reactions of 1,3-diazabuta-1,3-dienes with alkynyl ketenes

et al. 2009

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Section: Methodsmentioning

confidence: 99%

Cycloaddition reactions of 1,3-diazabuta-1,3-dienes with alkynyl ketenes

et al. 2009

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“…where, ρ k (N), ρ k (N − 1), and ρ k (N + 1) are the gross electronic population of atom k in neutral, cationic and anionic systems, respectively. 21,22 The local softness, s α k , can be readily calculated as follows:…”

Section: The Hsab Criterionmentioning

confidence: 99%

Regioselectivity in the hetero-Diels–Alder reactions of styrenes with 2-aza-1,3-butadiene: a DFT study

2017

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In this work, regioselectivity was investigated in the hetero-Diels-Alder reactions of styrenes (without substituent and with para-substituted groups) with 2-aza-1,3-butadiene from thermodynamic (Hammett study), electronic (HSAB criterion) and kinetic viewpoints. Furthermore, the effect of the presence of catalyst was inspected by the NBO analysis in addition to kinetic studies. The calculations were performed by the Gaussian 09 program at the B3LYP/6-311++G** level of theory in the gas phase. Thermodynamically, the stability difference between the two regioisomeric products is not significant, especially, in the reactions of styrenes with electron-releasing substituents. Kinetically, the obtained regioselectivity is in favor of formation of 4-regioisomers, especially, in the presence of BF 3 catalyst (in agreement with the NBO results). On the basis of the HSAB criterion, 5-regioisomers have preference, only in the reactions of styrenes with the strong electron-withdrawing substituents.

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“…The local softness, s a k , and local philicity index, o a k , condensed to atom k, are easily obtained by the global quantities and condensed Fukui functions in the molecule. Three different types of s a k and o a k can be readily defined as [39]:…”

Section: Local Descriptorsmentioning

confidence: 99%

Mechanism and Regioselectivity of the 1,3-Dipolar Cycloaddition of Methyleneamine N-Oxide with Cyclopent-3-Ene-1,2-Dione and its Aza, Oxa and Thia Analogues: A Dft Approach

Emamian

Zahedi

2012

Progress in Reaction Kinetics and Mechanism

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A theoretical study on the regioselectivity of 1,3-dipolar cycloaddition reactions between methyleneamine N-oxide (nitrone) and cyclopent-3-ene-1,2-dione (DPh1), pyrrole-2,3-dione (DPh2), furan-2,3-dione (DPh3) and thiophene-2,3dione (DPh4) has been carried out by means of several theoretical approaches, namely, activation energies, Houk's rule based on FMO theory and DFT reactivity indices. The calculations were performed at the DFT-B3LYP=6-31G(d) level of theory using Gaussian 03. The present analysis shows that these reactions have an NED character. Moreover, the results obtained from energetic and electronic approaches, with the exception of Gazquez -Mendez rule based on NPA analysis, confirm that 1,5-regioisomer is the major product.

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Elucidation of the substitutent effects on the reaction pathway of the cycloaddition of 1,3-diazabuta-1,3-dienes with ketenes using DFT-based reactivity indexes

Cited by 12 publications

References 31 publications

Cycloaddition reactions of 1,3-diazabuta-1,3-dienes with alkynyl ketenes

Cycloaddition reactions of 1,3-diazabuta-1,3-dienes with alkynyl ketenes

Regioselectivity in the hetero-Diels–Alder reactions of styrenes with 2-aza-1,3-butadiene: a DFT study

Mechanism and Regioselectivity of the 1,3-Dipolar Cycloaddition of Methyleneamine N-Oxide with Cyclopent-3-Ene-1,2-Dione and its Aza, Oxa and Thia Analogues: A Dft Approach

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