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A computational study of the mechanism of the unimolecular elimination of α,β-unsaturated aldehydes in the gas phase

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Abstract

The mechanism for the decarbonylation of (E)-2-butenal and (E)-2-methyl-3-pheny-2-propenal was studied with different levels of ab initio and DFT methods. Reactants, products and transition structures were optimized for two kinds of reaction channel: a one-step reaction which involves a three-membered cyclic transition state, and a two-step reaction which involves an initial four-membered cyclic transition state. According to our calculations, these two possible mechanisms entail similar energetic costs, and there are only small differences depending on the reactant. The elimination of (E)-2-methyl-3-pheny-2-propenal yields different products depending on the channel followed. Only one of the three possible one-step mechanisms leads directly to (E)-β-methylstyrene (the main product according to experiment). This fact is reasonably well reproduced by our results, since the corresponding transition state gave rise to the lowest activation Gibbs free energy.

Ab initio and DFT calculations have showed that elimination of (E)-2-butenal and (E)-2-methyl-3-pheny-2-propenal takes place through a three or a four-membered cyclic transition sate, with a one-step or a two-step mechanism, respectively.

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Acknowledgments

The authors thank the Xunta de Galicia for financial support (“Axuda para a Consolidación e Estructuración de unidades de investigación competitivas do Sistema Universitario de Galicia, 2007/50, cofinanciada polo FEDER 2007-2013”). The authors also wish to express their gratitude to the CESGA (Centro de Supercomputación de Galicia).

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Correspondence to Jesús Rodríguez-Otero.

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Geometries of reactants, products and transition structures (PDF 180 kb)

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Erastova, V., Rodríguez-Otero, J., Cabaleiro-Lago, E.M. et al. A computational study of the mechanism of the unimolecular elimination of α,β-unsaturated aldehydes in the gas phase. J Mol Model 17, 21–26 (2011). https://doi.org/10.1007/s00894-010-0700-1

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  • DOI: https://doi.org/10.1007/s00894-010-0700-1

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