Exploiting carbonyl groups to control intermolecular rhodium-catalyzed alkene and alkyne hydroacylation
<p>Readily available β-carbonyl-substituted aldehydes are shown to be exceptional substrates for Rh-catalyzed intermolecular alkene and alkyne hydroacylation reactions. By using cationic rhodium catalysts incorporating <i>bis</i>-phosphine ligands efficient and selective reactions...
| Main Authors: | , , , , , , |
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| Format: | Journal article |
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American Chemical Society
2017
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| _version_ | 1826300828934209536 |
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| author | Coxon, TJ Fernández, M Barwick-Silk, J Mckay, AI Britton, LE Weller, AS Willis, M |
| author_facet | Coxon, TJ Fernández, M Barwick-Silk, J Mckay, AI Britton, LE Weller, AS Willis, M |
| author_sort | Coxon, TJ |
| collection | OXFORD |
| description | <p>Readily available β-carbonyl-substituted aldehydes are shown to be exceptional substrates for Rh-catalyzed intermolecular alkene and alkyne hydroacylation reactions. By using cationic rhodium catalysts incorporating <i>bis</i>-phosphine ligands efficient and selective reactions are achieved for β-amido, β-ester and β-keto aldehyde substrates, providing a range of synthetically useful 1,3-dicarbonyl products in excellent yields. A correspondingly broad selection of alkenes and alkynes can be employed. For alkyne substrates, the use of a catalyst incorporating the Ampaphos ligand triggers a regioselectivity switch, allowing both linear and branched isomers to be prepared with high selectivity in an efficient manner. Structural data confirming aldehyde chelation, and a proposed mechanism, are provided.</p> |
| first_indexed | 2024-03-07T05:23:05Z |
| format | Journal article |
| id | oxford-uuid:df9ab9b4-9608-45ad-98e5-4bd051f2ed8b |
| institution | University of Oxford |
| last_indexed | 2024-03-07T05:23:05Z |
| publishDate | 2017 |
| publisher | American Chemical Society |
| record_format | dspace |
| spelling | oxford-uuid:df9ab9b4-9608-45ad-98e5-4bd051f2ed8b2022-03-27T09:40:35ZExploiting carbonyl groups to control intermolecular rhodium-catalyzed alkene and alkyne hydroacylationJournal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:df9ab9b4-9608-45ad-98e5-4bd051f2ed8bSymplectic Elements at OxfordAmerican Chemical Society2017Coxon, TJFernández, MBarwick-Silk, JMckay, AIBritton, LEWeller, ASWillis, M <p>Readily available β-carbonyl-substituted aldehydes are shown to be exceptional substrates for Rh-catalyzed intermolecular alkene and alkyne hydroacylation reactions. By using cationic rhodium catalysts incorporating <i>bis</i>-phosphine ligands efficient and selective reactions are achieved for β-amido, β-ester and β-keto aldehyde substrates, providing a range of synthetically useful 1,3-dicarbonyl products in excellent yields. A correspondingly broad selection of alkenes and alkynes can be employed. For alkyne substrates, the use of a catalyst incorporating the Ampaphos ligand triggers a regioselectivity switch, allowing both linear and branched isomers to be prepared with high selectivity in an efficient manner. Structural data confirming aldehyde chelation, and a proposed mechanism, are provided.</p> |
| spellingShingle | Coxon, TJ Fernández, M Barwick-Silk, J Mckay, AI Britton, LE Weller, AS Willis, M Exploiting carbonyl groups to control intermolecular rhodium-catalyzed alkene and alkyne hydroacylation |
| title | Exploiting carbonyl groups to control intermolecular rhodium-catalyzed alkene and alkyne hydroacylation |
| title_full | Exploiting carbonyl groups to control intermolecular rhodium-catalyzed alkene and alkyne hydroacylation |
| title_fullStr | Exploiting carbonyl groups to control intermolecular rhodium-catalyzed alkene and alkyne hydroacylation |
| title_full_unstemmed | Exploiting carbonyl groups to control intermolecular rhodium-catalyzed alkene and alkyne hydroacylation |
| title_short | Exploiting carbonyl groups to control intermolecular rhodium-catalyzed alkene and alkyne hydroacylation |
| title_sort | exploiting carbonyl groups to control intermolecular rhodium catalyzed alkene and alkyne hydroacylation |
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