Iridium-Catalyzed Enantioselective Intramolecular Hydroarylation of Allenes: Formal Synthesis of (+)-Rhazinilam
We report a versatile, highly enantioselective intramolecular hydroarylation of allenyl-tethered pyrroles and indoles. The reaction, promoted by an iridium(I)/bisphosphine chiral catalyst, provides a direct access heteropolycyclic systems bearing either tertiary or quaternary carbon stereocenters an...
| Autores: | , , , , |
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| Tipo de recurso: | artículo |
| Estado: | Versión publicada |
| Fecha de publicación: | 2025 |
| País: | España |
| Institución: | Consejo Superior de Investigaciones Científicas (CSIC) |
| Repositorio: | DIGITAL.CSIC. Repositorio Institucional del CSIC |
| OAI Identifier: | oai:digital.csic.es:10261/394246 |
| Acceso en línea: | http://hdl.handle.net/10261/394246 https://api.elsevier.com/content/abstract/scopus_id/105007438963 |
| Access Level: | acceso abierto |
| Palabra clave: | Allenes C–H activation Enantioselective Hydroarylation Iridium http://metadata.un.org/sdg/9 Build resilient infrastructure, promote inclusive and sustainable industrialization and foster innovation |
| Sumario: | We report a versatile, highly enantioselective intramolecular hydroarylation of allenyl-tethered pyrroles and indoles. The reaction, promoted by an iridium(I)/bisphosphine chiral catalyst, provides a direct access heteropolycyclic systems bearing either tertiary or quaternary carbon stereocenters and a synthetically appealing alkenyl pendant. The method allows a highly efficient assembly of five-, six- and even seven-membered fused indole and pyrrole products, providing enantiomeric excesses of up to 99%. DFT computational studies align nicely with the experimental results and allow to rationalize the key factors that control both regio- and stereoselectivity of the process. Finally, the synthetic potential of the method was exemplified with a very short, highly enantioselective formal synthesis of (+)-Rhazinilam. |
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