Next Article in Journal
Pd-Based Polysaccharide Hydrogels as Heterogeneous Catalysts for Oxidation of Aromatic Alcohols
Next Article in Special Issue
The Role of the Catalyst on the Reactivity and Mechanism in the Diels–Alder Cycloaddition Step of the Povarov Reaction for the Synthesis of a Biological Active Quinoline Derivative: Experimental and Theoretical Investigations
Previous Article in Journal / Special Issue
Application of β-Phosphorylated Nitroethenes in [3+2] Cycloaddition Reactions Involving Benzonitrile N-Oxide in the Light of a DFT Computational Study
Article

Theoretical Insight into the Reversal of Chemoselectivity in Diels-Alder Reactions of α,β-Unsaturated Aldehydes and Ketones Catalyzed by Brønsted and Lewis Acids

Laboratory of Applied Thermodynamics and Molecular Modeling, Department of Chemistry, Faculty of Science, University of Tlemcen, PB 119, Tlemcen 13000, Algeria
*
Author to whom correspondence should be addressed.
Academic Editor: Radomir Jasinski
Received: 29 December 2020 / Revised: 2 February 2021 / Accepted: 2 March 2021 / Published: 5 March 2021
(This article belongs to the Special Issue Cycloaddition Reaction in Organic Synthesis)
Experimentally, a reversal of chemoselectivity has been observed in catalyzed Diels–Alder reactions of α,β-unsaturated aldehydes (e.g., (2E)-but-2-enal) and ketones (e.g., 2-hexen-4-one) with cyclopentadiene. Indeed, using the triflimidic Brønsted acid Tf2NH as catalyst, the reaction gave a Diels–Alder adduct derived from α,β-unsaturated ketone as a major product. On the other hand, the use of tris(pentafluorophenyl)borane B(C6F5)3 bulky Lewis acid as catalyst gave mainly the cycloadduct of α,β-unsaturated aldehyde as a major product. Our aim in the present work is to put in evidence the role of the catalyst in the reversal of the chemoselectivity of the catalyzed Diels–Alder reactions of (2E)-but-2-enal and 2-Hexen-4-one with cyclopentadiene. The calculations were performed at the ωB97XD/6-311G(d,p) level of theory and the solvent effects of dichloromethane were taken into account using the PCM solvation model. The obtained results are in good agreement with experimental outcomes. View Full-Text
Keywords: Diels–Alder reaction; chemoselectivity; catalyst; Brønsted acid; Lewis acid; ωB97XD Diels–Alder reaction; chemoselectivity; catalyst; Brønsted acid; Lewis acid; ωB97XD
Show Figures

Figure 1

MDPI and ACS Style

Benhamed, L.; Mekelleche, S.M.; Benchouk, W. Theoretical Insight into the Reversal of Chemoselectivity in Diels-Alder Reactions of α,β-Unsaturated Aldehydes and Ketones Catalyzed by Brønsted and Lewis Acids. Organics 2021, 2, 38-49. https://0-doi-org.brum.beds.ac.uk/10.3390/org2010004

AMA Style

Benhamed L, Mekelleche SM, Benchouk W. Theoretical Insight into the Reversal of Chemoselectivity in Diels-Alder Reactions of α,β-Unsaturated Aldehydes and Ketones Catalyzed by Brønsted and Lewis Acids. Organics. 2021; 2(1):38-49. https://0-doi-org.brum.beds.ac.uk/10.3390/org2010004

Chicago/Turabian Style

Benhamed, Lakhdar, Sidi M. Mekelleche, and Wafaa Benchouk. 2021. "Theoretical Insight into the Reversal of Chemoselectivity in Diels-Alder Reactions of α,β-Unsaturated Aldehydes and Ketones Catalyzed by Brønsted and Lewis Acids" Organics 2, no. 1: 38-49. https://0-doi-org.brum.beds.ac.uk/10.3390/org2010004

Find Other Styles

Article Access Map by Country/Region

1
Back to TopTop