Palladium‐Catalyzed [3+2] Cycloadditions of Alkylidenecyclopropanes to Imines: A Direct Approach to Pyrrolidine Scaffolds
Abstract Alkylidenecyclopropanes (ACPs) can work as versatile 3 C partners in a range of [3+n] cycloadditions with unsaturated carbon partners. We now demonstrate that they can also be harnessed for inter‐ and intramolecular palladium‐catalyzed [3+2] formal cycloadditions with imines, offering a str...
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Wiley-VCH
2025-05-01
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| Online Access: | https://doi.org/10.1002/ceur.202500005 |
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| author | Ricardo Rodiño Felipe Verdugo José L. Mascareñas Fernando López |
| author_facet | Ricardo Rodiño Felipe Verdugo José L. Mascareñas Fernando López |
| author_sort | Ricardo Rodiño |
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| description | Abstract Alkylidenecyclopropanes (ACPs) can work as versatile 3 C partners in a range of [3+n] cycloadditions with unsaturated carbon partners. We now demonstrate that they can also be harnessed for inter‐ and intramolecular palladium‐catalyzed [3+2] formal cycloadditions with imines, offering a straightforward approach to constructing a diverse array of pyrrolidine scaffolds. The best results for the intermolecular variants are obtained using electron deficient imine partners, while the use of oxime ethers proved to be key for the intramolecular cases, which produce bicyclic pyrrolidine scaffolds. We also report preliminary results on enantioselective variants using palladium complexes bearing chiral phosphoramidite ligands. Finally, a DFT analysis provides relevant mechanistic insights, suggesting that the reactions proceed via pallada‐ene type of processes between initially generated palladacyclobutane and the C=N double bond of the imine partner. |
| format | Article |
| id | doaj-art-5ecff662efa34c978d1bc8aef69527bd |
| institution | OA Journals |
| issn | 2751-4765 |
| language | English |
| publishDate | 2025-05-01 |
| publisher | Wiley-VCH |
| record_format | Article |
| series | ChemistryEurope |
| spelling | doaj-art-5ecff662efa34c978d1bc8aef69527bd2025-08-20T02:30:32ZengWiley-VCHChemistryEurope2751-47652025-05-0133n/an/a10.1002/ceur.202500005Palladium‐Catalyzed [3+2] Cycloadditions of Alkylidenecyclopropanes to Imines: A Direct Approach to Pyrrolidine ScaffoldsRicardo Rodiño0Felipe Verdugo1José L. Mascareñas2Fernando López3Centro Singular de Investigación en Química Biolóxica e Materiais Moleculares (CIQUS) and Departamento de Química Orgánica Universidade de Santiago de Compostela (Spain) 15782 Santiago de Compostela SpainCentro Singular de Investigación en Química Biolóxica e Materiais Moleculares (CIQUS) and Departamento de Química Orgánica Universidade de Santiago de Compostela (Spain) 15782 Santiago de Compostela SpainCentro Singular de Investigación en Química Biolóxica e Materiais Moleculares (CIQUS) and Departamento de Química Orgánica Universidade de Santiago de Compostela (Spain) 15782 Santiago de Compostela SpainCentro Singular de Investigación en Química Biolóxica e Materiais Moleculares (CIQUS) and Departamento de Química Orgánica Universidade de Santiago de Compostela (Spain) 15782 Santiago de Compostela SpainAbstract Alkylidenecyclopropanes (ACPs) can work as versatile 3 C partners in a range of [3+n] cycloadditions with unsaturated carbon partners. We now demonstrate that they can also be harnessed for inter‐ and intramolecular palladium‐catalyzed [3+2] formal cycloadditions with imines, offering a straightforward approach to constructing a diverse array of pyrrolidine scaffolds. The best results for the intermolecular variants are obtained using electron deficient imine partners, while the use of oxime ethers proved to be key for the intramolecular cases, which produce bicyclic pyrrolidine scaffolds. We also report preliminary results on enantioselective variants using palladium complexes bearing chiral phosphoramidite ligands. Finally, a DFT analysis provides relevant mechanistic insights, suggesting that the reactions proceed via pallada‐ene type of processes between initially generated palladacyclobutane and the C=N double bond of the imine partner.https://doi.org/10.1002/ceur.202500005AlkylidenecyclopropanesCycloadditionImine palladiumPyrrolidines |
| spellingShingle | Ricardo Rodiño Felipe Verdugo José L. Mascareñas Fernando López Palladium‐Catalyzed [3+2] Cycloadditions of Alkylidenecyclopropanes to Imines: A Direct Approach to Pyrrolidine Scaffolds ChemistryEurope Alkylidenecyclopropanes Cycloaddition Imine palladium Pyrrolidines |
| title | Palladium‐Catalyzed [3+2] Cycloadditions of Alkylidenecyclopropanes to Imines: A Direct Approach to Pyrrolidine Scaffolds |
| title_full | Palladium‐Catalyzed [3+2] Cycloadditions of Alkylidenecyclopropanes to Imines: A Direct Approach to Pyrrolidine Scaffolds |
| title_fullStr | Palladium‐Catalyzed [3+2] Cycloadditions of Alkylidenecyclopropanes to Imines: A Direct Approach to Pyrrolidine Scaffolds |
| title_full_unstemmed | Palladium‐Catalyzed [3+2] Cycloadditions of Alkylidenecyclopropanes to Imines: A Direct Approach to Pyrrolidine Scaffolds |
| title_short | Palladium‐Catalyzed [3+2] Cycloadditions of Alkylidenecyclopropanes to Imines: A Direct Approach to Pyrrolidine Scaffolds |
| title_sort | palladium catalyzed 3 2 cycloadditions of alkylidenecyclopropanes to imines a direct approach to pyrrolidine scaffolds |
| topic | Alkylidenecyclopropanes Cycloaddition Imine palladium Pyrrolidines |
| url | https://doi.org/10.1002/ceur.202500005 |
| work_keys_str_mv | AT ricardorodino palladiumcatalyzed32cycloadditionsofalkylidenecyclopropanestoiminesadirectapproachtopyrrolidinescaffolds AT felipeverdugo palladiumcatalyzed32cycloadditionsofalkylidenecyclopropanestoiminesadirectapproachtopyrrolidinescaffolds AT joselmascarenas palladiumcatalyzed32cycloadditionsofalkylidenecyclopropanestoiminesadirectapproachtopyrrolidinescaffolds AT fernandolopez palladiumcatalyzed32cycloadditionsofalkylidenecyclopropanestoiminesadirectapproachtopyrrolidinescaffolds |