Platinum-catalyzed substitution of allylic fluorides
Allyl fluorides are reactive toward Pt-catalyzed alkylation with malonate and likewise toward N- and O-nucleophiles under mild conditions. The reactivity of fluoride as a leaving group equals or exceeds that of the esters and carbonates commonly employed in allylic alkylation. The order of leaving-g...
| Main Authors: | , , , , , |
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| Format: | Journal article |
| Language: | English |
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2012
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| _version_ | 1826269936724475904 |
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| author | Benedetto, E Keita, M Tredwell, M Hollingworth, C Brown, J Gouverneur, V |
| author_facet | Benedetto, E Keita, M Tredwell, M Hollingworth, C Brown, J Gouverneur, V |
| author_sort | Benedetto, E |
| collection | OXFORD |
| description | Allyl fluorides are reactive toward Pt-catalyzed alkylation with malonate and likewise toward N- and O-nucleophiles under mild conditions. The reactivity of fluoride as a leaving group equals or exceeds that of the esters and carbonates commonly employed in allylic alkylation. The order of leaving-group ability with Pt catalysts was found to be F ≥ OCO 2Me ≫ OBz ≥ OAc. This discouraged the application of platinum catalysts for the reverse reaction, fluorination of allylic substrates. Fluoride displacement involves predominant or complete retention of configuration in all the observed cases, and this was confirmed as a general feature of Pt catalysis, the stereochemical integrity being as high or higher as in Pd catalysis for the examples chosen. © 2012 American Chemical Society. |
| first_indexed | 2024-03-06T21:33:00Z |
| format | Journal article |
| id | oxford-uuid:454e29b7-2b4c-4b4d-9a62-acdb8b932119 |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-06T21:33:00Z |
| publishDate | 2012 |
| record_format | dspace |
| spelling | oxford-uuid:454e29b7-2b4c-4b4d-9a62-acdb8b9321192022-03-26T15:06:59ZPlatinum-catalyzed substitution of allylic fluoridesJournal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:454e29b7-2b4c-4b4d-9a62-acdb8b932119EnglishSymplectic Elements at Oxford2012Benedetto, EKeita, MTredwell, MHollingworth, CBrown, JGouverneur, VAllyl fluorides are reactive toward Pt-catalyzed alkylation with malonate and likewise toward N- and O-nucleophiles under mild conditions. The reactivity of fluoride as a leaving group equals or exceeds that of the esters and carbonates commonly employed in allylic alkylation. The order of leaving-group ability with Pt catalysts was found to be F ≥ OCO 2Me ≫ OBz ≥ OAc. This discouraged the application of platinum catalysts for the reverse reaction, fluorination of allylic substrates. Fluoride displacement involves predominant or complete retention of configuration in all the observed cases, and this was confirmed as a general feature of Pt catalysis, the stereochemical integrity being as high or higher as in Pd catalysis for the examples chosen. © 2012 American Chemical Society. |
| spellingShingle | Benedetto, E Keita, M Tredwell, M Hollingworth, C Brown, J Gouverneur, V Platinum-catalyzed substitution of allylic fluorides |
| title | Platinum-catalyzed substitution of allylic fluorides |
| title_full | Platinum-catalyzed substitution of allylic fluorides |
| title_fullStr | Platinum-catalyzed substitution of allylic fluorides |
| title_full_unstemmed | Platinum-catalyzed substitution of allylic fluorides |
| title_short | Platinum-catalyzed substitution of allylic fluorides |
| title_sort | platinum catalyzed substitution of allylic fluorides |
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