Intramolecular [3 + 2] Cycloaddition Reactions of Unsaturated Nitrile Oxides. A Study from the Perspective of Bond Evolution Theory (BET)
- Abel Idrice Adjieufack
Abel Idrice AdjieufackPhysical and Theoretical Chemistry of Laboratory, University of Yaoundé 1, Yaoundé, CameroonLaboratory of Theoretical Chemistry (LCT) and Namur Institute of Structured Matter (NISM), University of Namur, Rue de Bruxelles, 61, B-5000 Namur, BelgiumMore by Abel Idrice Adjieufack
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- Vincent Liégeois*
Vincent Liégeois*E-mail: [email protected]Laboratory of Theoretical Chemistry (LCT) and Namur Institute of Structured Matter (NISM), University of Namur, Rue de Bruxelles, 61, B-5000 Namur, BelgiumMore by Vincent Liégeois
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- Ibrahim Ndassa Mboumbouo
Ibrahim Ndassa MboumbouoDepartment of Chemistry, High Teacher Training College, University of Yaoundé 1, Yaoundé, CameroonMore by Ibrahim Ndassa Mboumbouo
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- Joseph Ketcha Mbadcam
Joseph Ketcha MbadcamPhysical and Theoretical Chemistry of Laboratory, University of Yaoundé 1, Yaoundé, CameroonMore by Joseph Ketcha Mbadcam
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- Benoît Champagne
Benoît ChampagneLaboratory of Theoretical Chemistry (LCT) and Namur Institute of Structured Matter (NISM), University of Namur, Rue de Bruxelles, 61, B-5000 Namur, BelgiumMore by Benoît Champagne
Abstract
The reaction mechanism of the [3 + 2] intramolecular cycloaddition of 3,3-dimethyl-2-(prop-2-en-1-yloxy) and (prop-2-en-1-ylsulfanyl) nitrile oxides is analyzed using different DFT functionals with the 6-311++G(d,p) basis set. The activation and the reaction energies for the cis and trans pathways are evaluated at the DFT, MP2, and CCSD(T) levels of theory as well as their Gibbs free energy counterparts. It is shown that the trans regioisomers are both thermodynamic and kinetic compounds, in agreement with experimental outcomes. For a deeper understanding of the reaction mechanism, a BET analysis along the reaction channel (trans and cis) has been carried out. This analysis reveals that the lone pair on the nitrogen atom is formed first, then the C–C bond, and finally the O–C one. The global mechanism is similar for the two compounds and for the two pathways even if some small differences are observed, for instance, in the values of the reaction coordinates of appeareance of the different basins.
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