This paper describes the first detailed computational mechanistic study of the Julia-Kocieński olefination between acetaldehyde (1) and ethyl 1-phenyl-1H-tetrazol-5-yl sulfone (2), considered a paradigmatic example of the reaction between unsubstituted alkyl PT sulfones and linear aliphatic aldehydes. The theoretical study was performed within the density functional approach through calculations at the B3LYP/6-311+G(d,p) level for all atoms except sulfur for which the 6-311+G(2df,p) basis set was used. All the different intermediates and transition states encountered along the reaction pathways leading to final E and Z olefins have been located and the relative energies calculated, both for the reactions with potassium- and lithium-metalated sulfones, in THF and toluene, respectively. We have essentially confirmed the complex multistep mechanistic manifold proposed by others; however, the formation of a spirocyclic intermediate in the Smiles rearrangement was excluded. Instead, we found that this step involves a concerted, though asynchronous, mechanism. Moreover, our calculations nicely fit with the diastereoselectivities observed experimentally for potassium- and lithium-metalated sulfones, in THF and toluene, respectively.

Legnani, L., Porta, A., Caramella, P., Toma, L., Zanoni, G., Vidari, G. (2015). Computational mechanistic study of the julia-kocieński reaction. JOURNAL OF ORGANIC CHEMISTRY, 80(6), 3092-3100 [10.1021/acs.joc.5b00008].

Computational mechanistic study of the julia-kocieński reaction

LEGNANI, LAURA
;
2015

Abstract

This paper describes the first detailed computational mechanistic study of the Julia-Kocieński olefination between acetaldehyde (1) and ethyl 1-phenyl-1H-tetrazol-5-yl sulfone (2), considered a paradigmatic example of the reaction between unsubstituted alkyl PT sulfones and linear aliphatic aldehydes. The theoretical study was performed within the density functional approach through calculations at the B3LYP/6-311+G(d,p) level for all atoms except sulfur for which the 6-311+G(2df,p) basis set was used. All the different intermediates and transition states encountered along the reaction pathways leading to final E and Z olefins have been located and the relative energies calculated, both for the reactions with potassium- and lithium-metalated sulfones, in THF and toluene, respectively. We have essentially confirmed the complex multistep mechanistic manifold proposed by others; however, the formation of a spirocyclic intermediate in the Smiles rearrangement was excluded. Instead, we found that this step involves a concerted, though asynchronous, mechanism. Moreover, our calculations nicely fit with the diastereoselectivities observed experimentally for potassium- and lithium-metalated sulfones, in THF and toluene, respectively.
Articolo in rivista - Articolo scientifico
Acetaldehyde; Alkenes; Molecular Structure; Sulfones; Quantum Theory; Organic Chemistry; Medicine (all);
English
3092
3100
9
Legnani, L., Porta, A., Caramella, P., Toma, L., Zanoni, G., Vidari, G. (2015). Computational mechanistic study of the julia-kocieński reaction. JOURNAL OF ORGANIC CHEMISTRY, 80(6), 3092-3100 [10.1021/acs.joc.5b00008].
Legnani, L; Porta, A; Caramella, P; Toma, L; Zanoni, G; Vidari, G
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/10281/352042
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