Asymmetric Transfer of Carbenes with Phenyliodonium Ylides
Phenyliodonium ylides, readily available upon treatment of CH-acidic compounds such 1,3-dicarbonyl derivatives with iodobenzene diacetate, react in the presence of rhodium(II) or copper catalysts to afford products derived from carbenoid pathways. Chemo- and enantioselectivity of the reactions are i...
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| Published in | Accounts of chemical research Vol. 37; no. 4; pp. 243 - 251 |
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| Main Author | |
| Format | Journal Article |
| Language | English |
| Published |
United States
American Chemical Society
01.04.2004
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| Online Access | Get full text |
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| Summary: | Phenyliodonium ylides, readily available upon treatment of CH-acidic compounds such 1,3-dicarbonyl derivatives with iodobenzene diacetate, react in the presence of rhodium(II) or copper catalysts to afford products derived from carbenoid pathways. Chemo- and enantioselectivity of the reactions are identical to those of the corresponding diazocompounds, indicating metallocarbene intermediates with both precursors. An exception to this occurs in the intramolecular cyclopropanation of phenyliodonium ylides, where a competing uncatalyzed pathway intervenes at room temperature. When phenyliodonium ylides are generated in the presence of Rh(II) catalysts and olefins, they react in situ to afford cyclopropanes. |
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| Bibliography: | ark:/67375/TPS-7DFP9CRV-P istex:486493067108AC2B308AD84DB543B291E27A9381 ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 |
| ISSN: | 0001-4842 1520-4898 |
| DOI: | 10.1021/ar0202619 |