Rhodium-catalyzed intermolecular chelation controlled alkene and alkyne hydroacylation: synthetic scope of beta-S-substituted aldehyde substrates.
The use of beta-S-substituted aldehydes in rhodium-catalyzed intermolecular hydroacylation reactions is reported. Aldehydes substituted with either sulfide or thioacetal groups undergo efficient hydroacylation with a variety of electron-poor alkenes, such as enoates, in Stetter-like processes and wi...
| Main Authors: | , , , , |
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| 格式: | Journal article |
| 语言: | English |
| 出版: |
2006
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| _version_ | 1826305251664199680 |
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| author | Willis, M Randell-Sly, H Woodward, R McNally, S Currie, G |
| author_facet | Willis, M Randell-Sly, H Woodward, R McNally, S Currie, G |
| author_sort | Willis, M |
| collection | OXFORD |
| description | The use of beta-S-substituted aldehydes in rhodium-catalyzed intermolecular hydroacylation reactions is reported. Aldehydes substituted with either sulfide or thioacetal groups undergo efficient hydroacylation with a variety of electron-poor alkenes, such as enoates, in Stetter-like processes and with both electron-poor and neutral alkynes. In general, the reactions with electron-poor alkenes demonstrate good selectivity for the linear regioisomer, and the reactions with alkynes provide enone products with excellent selectivity for the E-isomers. The scope of the process was shown to be broad, tolerating a variety of substitution patterns and functional groups on both reaction components. A novel CN-directing effect was shown to be responsible for reversing the regioselectivity in a number of alkyne hydroacylation reactions. Catalyst loadings as low as 0.1 mol % were achievable. |
| first_indexed | 2024-03-07T06:30:05Z |
| format | Journal article |
| id | oxford-uuid:f5b1710c-a10c-446d-a93f-ca94d59e899a |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-07T06:30:05Z |
| publishDate | 2006 |
| record_format | dspace |
| spelling | oxford-uuid:f5b1710c-a10c-446d-a93f-ca94d59e899a2022-03-27T12:29:14ZRhodium-catalyzed intermolecular chelation controlled alkene and alkyne hydroacylation: synthetic scope of beta-S-substituted aldehyde substrates.Journal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:f5b1710c-a10c-446d-a93f-ca94d59e899aEnglishSymplectic Elements at Oxford2006Willis, MRandell-Sly, HWoodward, RMcNally, SCurrie, GThe use of beta-S-substituted aldehydes in rhodium-catalyzed intermolecular hydroacylation reactions is reported. Aldehydes substituted with either sulfide or thioacetal groups undergo efficient hydroacylation with a variety of electron-poor alkenes, such as enoates, in Stetter-like processes and with both electron-poor and neutral alkynes. In general, the reactions with electron-poor alkenes demonstrate good selectivity for the linear regioisomer, and the reactions with alkynes provide enone products with excellent selectivity for the E-isomers. The scope of the process was shown to be broad, tolerating a variety of substitution patterns and functional groups on both reaction components. A novel CN-directing effect was shown to be responsible for reversing the regioselectivity in a number of alkyne hydroacylation reactions. Catalyst loadings as low as 0.1 mol % were achievable. |
| spellingShingle | Willis, M Randell-Sly, H Woodward, R McNally, S Currie, G Rhodium-catalyzed intermolecular chelation controlled alkene and alkyne hydroacylation: synthetic scope of beta-S-substituted aldehyde substrates. |
| title | Rhodium-catalyzed intermolecular chelation controlled alkene and alkyne hydroacylation: synthetic scope of beta-S-substituted aldehyde substrates. |
| title_full | Rhodium-catalyzed intermolecular chelation controlled alkene and alkyne hydroacylation: synthetic scope of beta-S-substituted aldehyde substrates. |
| title_fullStr | Rhodium-catalyzed intermolecular chelation controlled alkene and alkyne hydroacylation: synthetic scope of beta-S-substituted aldehyde substrates. |
| title_full_unstemmed | Rhodium-catalyzed intermolecular chelation controlled alkene and alkyne hydroacylation: synthetic scope of beta-S-substituted aldehyde substrates. |
| title_short | Rhodium-catalyzed intermolecular chelation controlled alkene and alkyne hydroacylation: synthetic scope of beta-S-substituted aldehyde substrates. |
| title_sort | rhodium catalyzed intermolecular chelation controlled alkene and alkyne hydroacylation synthetic scope of beta s substituted aldehyde substrates |
| work_keys_str_mv | AT willism rhodiumcatalyzedintermolecularchelationcontrolledalkeneandalkynehydroacylationsyntheticscopeofbetassubstitutedaldehydesubstrates AT randellslyh rhodiumcatalyzedintermolecularchelationcontrolledalkeneandalkynehydroacylationsyntheticscopeofbetassubstitutedaldehydesubstrates AT woodwardr rhodiumcatalyzedintermolecularchelationcontrolledalkeneandalkynehydroacylationsyntheticscopeofbetassubstitutedaldehydesubstrates AT mcnallys rhodiumcatalyzedintermolecularchelationcontrolledalkeneandalkynehydroacylationsyntheticscopeofbetassubstitutedaldehydesubstrates AT currieg rhodiumcatalyzedintermolecularchelationcontrolledalkeneandalkynehydroacylationsyntheticscopeofbetassubstitutedaldehydesubstrates |