Insights into the mechanism and regiochemistry of the 1,3-dipolar cycloaddition reaction between benzaldehyde and diazomethane

Abbiche, Khalid; Mohammad‐Salim, Haydar A.; Salah, Mohammed; Mazoir, Noureddine; Zeroual, Abdellah; Abdallaoui, Habib El Alaoui El; Hammadi, Abdellatif El; Hilali, Mustapha; Abdallah, Hassan H.; Hochlaf, M.

doi:10.1007/s00214-020-02662-4

Cited by 24 publications

(10 citation statements)

References 66 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…For polar 32CA reactions, the most favorable regioisomeric reaction path involves the two‐center interaction between the strongest electrophilic and the strongest nucleophilic centers of the reactants. Several studies dealing with 32CA reactions, 14,64,65 in particular reactions with a strong polar character, showed that the experimentally observed regioselectivity can be related to the electrophilic and nucleophilic Parr functions 49 . Thus, the nucleophilic P k − and electrophilic P k + Parr functions of N‐benzyl fluoro nitrone ( a ) and of 1b , 2b , and 3b maleimides were analyzed.…”

Section: Resultsmentioning

confidence: 99%

Insights into the mechanism of [3+2] cycloaddition reactions between N‐benzyl fluoro nitrone and maleimides, its selectivity and solvent effects

Boutiddar,

Abbiche,

Mellaoui

et al. 2023

J Comput Chem

View full text Add to dashboard Cite

We present a theoretical study of the [3+2] cycloaddition (32CA) reactions of N‐benzyl fluoro nitrone with a series of maleimides producing isoxazolidines. We use the Molecular Electron Density Theory at the MPWB1K/6‐311G(d) level. We focus on the reaction mechanism, selectivity, solvent, and temperature effects. In addition, we perform topological analyses at the minimal and transition states to identify the intermolecular interactions. Electron Localization Function approach classifies the N‐benzyl fluoro nitrone as zwitterionic (zw‐) three‐atom components (TACs), associated with a high energy barrier. The low polar character of the reaction is evaluated using the Conceptual Density Functional Theory analysis of the reactants, confirmed by the low global electron density transfer computed at the transition states. Computations show that these 32CA reactions follow a one‐step mechanism under kinetic control, with highly asynchronous bond formation and no new covalent bond is formed at the TS. Besides, the potential energy surfaces along the reaction pathways in gas phase and in solvent are mapped. The corresponding Gibbs free energy profiles reveal that the exo‐cycloadducts are kinetically and thermodynamically more favored than endo‐cycloadducts, in agreement with the exo‐selectivity observed experimentally. In particular, we found that solvent and temperature did not affect this selectivity and mainly influence the activation energies and the exothermic character of these 32CA reactions.

show abstract

Section: Resultsmentioning

confidence: 99%

Insights into the mechanism of [3+2] cycloaddition reactions between N‐benzyl fluoro nitrone and maleimides, its selectivity and solvent effects

Boutiddar,

Abbiche,

Mellaoui

et al. 2023

J Comput Chem

View full text Add to dashboard Cite

show abstract

“…The ELF establishes a direct quantitative connection between the electron density distribution and the chemical structure [36][37][38][39][40][41][42][43]. Herein, the reactivity of reactants in dimerization reactions is studied from the ELF topological analysis.…”

Section: Elf Topological Analysis Of Reactantsmentioning

confidence: 99%

Дослідження Фотохімічної Димеризації 3-Гетероарил (Фурил, Тіофіл, Селенофіл І Телурофіл)-Акрилатів Методом DFT

Джалал

Абдаллах²

2021

J. of Chem. and Tech.

View full text Add to dashboard Cite

На основі всебічного огляду фотохімічних димеризацій різних 3-гетероарил(фурил, тіофіл, селенофіл і телурофіл)-акрилатів було представлено докладне теоретичне пояснення спостережуваної фотохімічної реакції сполук даного типу. Теорія функціоналу густини (DFT) була використана для вивчення механізму реакції і визначення місця розташування всіх проміжних і перехідних станів уздовж кривої потенційної енергії. Розраховані енергетичні бар'єри були використані для порівняння стабільності різних конформацій. Реакції показали гарну регіо - та стереоселективність за рахунок утворення бірадикального перехідного стану. Для обґрунтування результатів найбільш стабільних ізомерів було виконано порівняння значень глобальної електрофільності, нуклеофільності, жорсткості, м'якості і потенціалу іонізації. Крім того, для найбільш стабільних продуктів були проаналізовані частоти ІЧ-коливань, енергетичні параметри та виконаний аналіз молекулярних орбіталей.

show abstract

“…To determine the impact of variations in electron density on molecular reactivity, Domingo presented the molecular electron density theory (MEDT) in 2016 [6]. Analysis of the experimentally observed reactivity, region, stereo-and chemoselectivity, catalysis, strain promotion, substituent effects, and other aspects of 32CA reactions have all benefited from the MEDT perspective over the past seven years [7][8][9][10][11][12]. Recently, the MEDT viewpoint has also been used to report on the successful interaction between experiment and theory in many 32CA reactions [13][14][15][16][17][18][19][20][21].…”

Section: Introductionmentioning

confidence: 99%

Expounding the Mechanism and Regioselectvity of [3+2] Cycloloaddition between N-phenylmethanimine oxide Nitrone and 2-methylene-1,3-dithiolane 1,3-dioxide

Aitouna

Barhoumi

Zeroual

et al. 2023

Preprint

View full text Add to dashboard Cite

The molecular electron density theory (MEDT) framework has been used to analyze the [3 + 2] cycloaddition reaction (32CA) between 2-methylene-1,3-dithiolane 1,3-dioxide MDD-2 and N-phenylmethanimine oxide nitrone NIT-1 at the B3LYP/6-311 + + G(d,p) level of theory. The Parr functions and the energy studies clearly reveal that this reaction is extremely regioselective, which is in perfect agreement with the experimental results. This 32CA zwitter-ionic type reaction exhibits high free energies of activation between 21.23 and 23.03 kcal mol-1. By analyzing the chemical mechanism in terms of bond evolution theory (BET), which discloses a variety of fluctuations in the electron density along the reaction route, a one-step mechanism with extremely asynchronous transition states is revealed.

show abstract

Insights into the mechanism and regiochemistry of the 1,3-dipolar cycloaddition reaction between benzaldehyde and diazomethane

Cited by 24 publications

References 66 publications

Insights into the mechanism of [3+2] cycloaddition reactions between N‐benzyl fluoro nitrone and maleimides, its selectivity and solvent effects

Insights into the mechanism of [3+2] cycloaddition reactions between N‐benzyl fluoro nitrone and maleimides, its selectivity and solvent effects

Дослідження Фотохімічної Димеризації 3-Гетероарил (Фурил, Тіофіл, Селенофіл І Телурофіл)-Акрилатів Методом DFT

Expounding the Mechanism and Regioselectvity of [3+2] Cycloloaddition between N-phenylmethanimine oxide Nitrone and 2-methylene-1,3-dithiolane 1,3-dioxide

Contact Info

Product

Resources

About