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Abstract
The [3+2] cycloaddition (32CA) reaction between difluoromethyl diazomethane (DFDAM) and 3-ylideneoxindole (3YOI) has been studied using molecular electron density theory at the M06-2X/6-311+G(d,p) computational level. ELF topological analysis of DFDAM characterizes this three-atom-component (TAC) as a pseudoradical species participating in the pseudomonoradical (pmr)-type 32CA reactions. Analysis of the conceptual DFT reactivity indices indicates that along a polar reaction 3YOI will act as the electrophile while DFDAM will act as the nucleophile. This 32CA reaction presents low activation enthalpy in dichloromethane, 8.2 kcal mol−1. The reaction is endo selective and completely ortho regioselective in agreement with the experimental outcome. The strong exergonic character of this 32CA reaction, −18.9 kcal mol−1, makes it irreversible. The high global electron density transfer found at the most favorable ortho/endo TS, 0.24e, accounts for the highly polar character of this 32CA reaction, classified as the forward electron density flux. BET analysis along the most favourable ortho/endo reaction path asserts the pmr-type reactivity of this TAC. This 32CA reaction takes place through a non-concerted two-stage one-step mechanism characterized by the initial C-C single bond formation involving the pseudoradical C3 carbon of DFDAM.
Original language | English |
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Pages (from-to) | 18652-18663 |
Number of pages | 12 |
Journal | New Journal of Chemistry |
Volume | 46 |
Issue number | 39 |
DOIs | |
Publication status | Published - 5 Sept 2022 |
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Dive into the research topics of 'Unveiling the [3+2] cycloaddition between difluoromethyl diazomethane and 3-ylideneoxindole from the perspective of molecular electron density theory'. Together they form a unique fingerprint.Projects
- 2 Finished
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Equipment renewal for the Consortium des Equipements de Calcul Intensif (CECI)
Bontempi, G., Champagne, B., Geuzaine , C., RIGNANESE, G. M. & Lazzaroni, R.
1/01/22 → 31/12/23
Project: Research
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CÉCI – Consortium of high performance computing centers
Champagne, B., Lazzaroni, R., Geuzaine , C., Chatelain, P. & Knaepen, B.
1/01/18 → 31/12/22
Project: Research
Equipment
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High Performance Computing Technology Platform
Benoît Champagne (Manager)
Technological Platform High Performance ComputingFacility/equipment: Technological Platform