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Lewis acid-catalyzed Diels–Alder cycloaddition of 2,5-dimethylfuran and ethylene: a density functional theory investigation

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Abstract

Density functional theory calculations with the M06-2X exchange–correlation functional have been performed to explore the Diels–Alder reaction between 2,5-DMF and ethylene as well as to compare the uncatalyzed reaction to the one catalyzed by the AlCl3 Lewis acid. The uncatalyzed reaction corresponds to a normal electron-demand (NED) mechanism where ethylene is an electron acceptor and 2,5-DMF plays the role of electron donor. This reaction presents a low polar character, its kinetics is little impacted by the solvent dielectric constant, and the formation of the two new σ bonds occurs through a one-step synchronous process. When the LA interacts with ethylene, forming a π-complex, it enhances its acceptor character, further favoring the NED mechanism, which is accompanied by a reduction of the free energy of the transition state. On the other hand, when AlCl3 is complexed by 2,5-DMF, the inverse electron-demand (IED) mechanism is favored, with ethylene playing the role of the donor. Within both NED and IED mechanism, the LA-catalyzed reaction takes place via a one-step asynchronous process. In addition, it is highly polar, so that the activation barrier decreases with the solvent polarity. Moreover, the calculations have evidenced that the LA forms stable complexes with any of the reactants so that the gain on the activation barrier amounts to 9–12 kcal mol−1 for the NED mechanism and to 3–9 kcal mol−1 for the IED one and that the formation of Al2Cl6 dimers impacts the different equilibria. Finally, the decrease of the activation barrier goes in pair with the reduction of the HOMO–LUMO gap, with the greatest decrease recorded when the LA interacts with ethylene according to the NED mechanism.

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Acknowledgements

The authors are grateful to the Ministry of Higher Education and Scientific Research of Tunisia, which financially supported this work. M.C. is grateful to UNamur for financially contributing to his research stay. The calculations were performed on the computers of the « Consortium des équipements de Calcul Intensif (CÉCI) » (http://www.ceci-hpc.be), including those of the « UNamur Technological Platform of High-Performance Computing (PTCI) » (http://www.ptci.unamur.be), for which we gratefully acknowledge the financial support from the FNRS-FRFC, the Walloon Region, and the University of Namur (Conventions No. 2.5020.11, GEQ U.G006.15, U.G018.19, 1610468, and RW/GEQ2016).

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Authors and Affiliations

  1. Laboratory of Organic Chemistry (LR17ES08), Faculty of Sciences, University of Sfax, 3038, Sfax, Tunisia

    Mohamed Chellegui & Mahmoud Trabelsi

  2. Laboratory of Theoretical Chemistry, Theoretical and Structural Physical Chemistry Unit, NISM (Namur Institute of Structured Matter), University of Namur, rue de Bruxelles, 61, 5000, Namur, Belgium

    Mohamed Chellegui & Benoît Champagne

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Correspondence to Benoît Champagne.

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214_2022_2880_MOESM1_ESM.pdf

Supplementary file1 The list of thermochemical data calculated with different exchange-correlation functionals, conceptual DFT descriptors of the reactants, frontier molecular orbital diagrams of the uncatalyzed and LA-catalyzed DA reactions between 2,5-DMF and ethylene in solution (1,4-dioxane, chloroform, and acetonitrile), thermochemical data of the AlCl3 complexation reaction with solvent molecules and with the O atom of 2,5-DMF, as well as energies, enthalpies, free enthalpies and entropies of the reactants, products and TSs are given in the SI.pdf file. (PDF 1981 kb)

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Chellegui, M., Champagne, B. & Trabelsi, M. Lewis acid-catalyzed Diels–Alder cycloaddition of 2,5-dimethylfuran and ethylene: a density functional theory investigation. Theor Chem Acc 141, 21 (2022). https://doi.org/10.1007/s00214-022-02880-y

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