Alkene-directed, nickel-catalyzed alkyne coupling reactions
| Autor: | Karen M. Miller, Torsak Luanphaisarnnont, Timothy F. Jamison, Carmela Molinaro |
|---|---|
| Rok vydání: | 2004 |
| Předmět: |
chemistry.chemical_classification
Allylic rearrangement Alkene Aryl Substituent Alkyne Regioselectivity General Chemistry General Medicine Biochemistry Aldehyde Medicinal chemistry Catalysis Coupling reaction chemistry.chemical_compound Colloid and Surface Chemistry chemistry Organic chemistry Organic synthesis |
| Zdroj: | Journal of the American Chemical Society. 126(13) |
| ISSN: | 0002-7863 |
| Popis: | In alkene-directed, nickel-catalyzed coupling reactions of 1,3-enynes with aldehydes and epoxides, the conjugated alkene dramatically enhances reactivity and uniformly directs regioselectivity, independent of the nature of the other alkyne substituent (aryl, alkyl (1 degrees , 2 degrees , 3 degrees )) or the degree of alkene substitution (mono-, di-, tri-, and tetrasubstituted). These observations are best explained by a temporary interaction between the alkene and the transition metal center during the regioselectivity-determining step. The highly substituted 1,3-diene products are useful in organic synthesis and, in conjunction with a Rh-catalyzed, site-selective hydrogenation, afford allylic and homoallylic alcohols that previously could not be prepared in high regioselectivity (or at all) with related Ni-catalyzed alkyne coupling reactions. |
| Databáze: | OpenAIRE |
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