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Theoretical Insight into the Reversal of Chemoselectivity in Diels-Alder Reactions of α,β-Unsaturated Aldehydes and Ketones Catalyzed by Brønsted and Lewis Acids
| Content Provider | MDPI |
|---|---|
| Author | Benhamed, Lakhdar Mekelleche, Sidi Benchouk, Wafaa |
| Copyright Year | 2021 |
| Description | 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. |
| Ending Page | 49 |
| Page Count | 12 |
| Starting Page | 38 |
| e-ISSN | 2673401X |
| DOI | 10.3390/org2010004 |
| Journal | Organics |
| Issue Number | 1 |
| Volume Number | 2 |
| Language | English |
| Publisher | MDPI |
| Publisher Date | 2021-03-05 |
| Access Restriction | Open |
| Subject Keyword | Organics Organic Chemistry Diels–alder Reaction Chemoselectivity Catalyst Brønsted Acid Lewis Acid Ωb97xd |
| Content Type | Text |
| Resource Type | Article |
