[3+2] Cycloaddition reaction of 1H-phosphorinium-3-olate and 1-methylphosphorinium-3-olate with methyl acrylate: A DFT study
| Autor: | Ibrahim A. Alswaidan, Mar Ríos-Gutiérrez, Dhanashree Hallooman, Luis R. Domingo, Ponnadurai Ramasami, Lydia Rhyman, Hoong-Kun Fun |
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| Rok vydání: | 2016 |
| Předmět: |
Ethanol
010405 organic chemistry Hydrogen bond Regioselectivity chemistry.chemical_element 010402 general chemistry Condensed Matter Physics Photochemistry 01 natural sciences Biochemistry Nitrogen Transition state Cycloaddition 0104 chemical sciences chemistry.chemical_compound chemistry Computational chemistry Density functional theory Physical and Theoretical Chemistry Methyl acrylate |
| Zdroj: | Computational and Theoretical Chemistry. 1087:36-47 |
| ISSN: | 2210-271X |
| Popis: | A density functional theory study was performed on the [3+2] cycloaddition (32CA) reaction of 1H-phosphorinium-3-olate and 1-methylphosphorinium-3-olate with methyl acrylate. The thermodynamic and kinetic parameters were analysed by considering the regio- and stereoisomeric pathways in gas phase and solvents. The geometries indicate that the transition states are slightly more advanced and asynchronous in ethanol. Electron localisation function topological analysis of the bonding changes along the most favourable reaction pathway associated with the 32CA reaction of 1H-phosphorinium-3-olate with methyl acrylate indicates that the reaction takes place through a two-stage one-step mechanism. Non-covalent interactions analysis of TS6x-H reveals the existence of weak hydrogen bonding explaining the regioselectivity found in this low-polar zw-type 32CA reaction. On comparing these theoretical findings with the nitrogen analogues of the 32CA reactions, it is found that the regioselectivity is affected and the pathways are kinetically and thermodynamically enhanced. Therefore, a priori, the phosphorus cycloadducts could be synthesised. |
| Databáze: | OpenAIRE |
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