Intramolecular [3 + 2] Cycloaddition Reactions of Unsaturated Nitrile Oxides. A Study from the Perspective of Bond Evolution Theory (BET)

Abel Idrice Adjieufack; Vincent Liégeois; Ibrahim Mbouombouo Ndassa; Joseph Ketcha Mbadcam; Benoît Champagne

doi:10.1021/acs.jpca.8b06711

Intramolecular [3 + 2] Cycloaddition Reactions of Unsaturated Nitrile Oxides. A Study from the Perspective of Bond Evolution Theory (BET)

Abel Idrice Adjieufack, Vincent Liégeois, Ibrahim Mbouombouo Ndassa, Joseph Ketcha Mbadcam, Benoît Champagne

Research output: Contribution to journal › Article

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.

Original language	English
Pages (from-to)	7472-7481
Number of pages	10
Journal	Journal of physical chemistry A
Volume	122
Issue number	37
DOIs	https://doi.org/10.1021/acs.jpca.8b06711
Publication status	Published - 20 Sep 2018

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Projects

1 Active
2 Finished

consortium des équipements de calcul intensif

CHAMPAGNE, B.

1/01/11 → 31/12/20

Project: Research

CÉCI – Consortium of high performance computing centers

CHAMPAGNE, B., Lazzaroni, R., Geuzaine , C., Chatelain, P. & Knaepen, B.

1/01/18 → 31/12/19

Project: Research

Density Functional Theory Study of 1,3-Dipolar Cycloadditions Reactions

CHAMPAGNE, B. & Adjieufack, A. I.

1/11/17 → 31/10/18

Project: Research

Equipment

High Performance Computing Technology Platform

Benoît Champagne (Manager)

Technological Platform High Performance Computing

Facility/equipment: Technological Platform

Cite this

Adjieufack, A. I., Liégeois, V., Mbouombouo Ndassa, I., Ketcha Mbadcam, J., & Champagne, B. (2018). Intramolecular [3 + 2] Cycloaddition Reactions of Unsaturated Nitrile Oxides. A Study from the Perspective of Bond Evolution Theory (BET). Journal of physical chemistry A, 122(37), 7472-7481. https://doi.org/10.1021/acs.jpca.8b06711

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Intramolecular [3 + 2] Cycloaddition Reactions of Unsaturated Nitrile Oxides. A Study from the Perspective of Bond Evolution Theory (BET). / Adjieufack, Abel Idrice ; Liégeois, Vincent; Mbouombouo Ndassa, Ibrahim; Ketcha Mbadcam, Joseph; Champagne, Benoît.

In: Journal of physical chemistry A, Vol. 122, No. 37, 20.09.2018, p. 7472-7481.

Research output: Contribution to journal › Article

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