The final steps of the Oppolzer cyclization: mechanism of the insertion of alkenes into allylpalladium(II) complexes |
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Authors: | Cárdenas Diego J Alcamí Manuel Cossío Fernando Méndez María Echavarren Antonio M |
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Affiliation: | Departamento de Química Orgánica, Universidad Autónoma de Madrid, Cantoblanco, 28049 Madrid, Spain. |
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Abstract: | We report here the results of a computational study on the the mechanism of the Oppolzer cyclization. These results lead us to conclude that the insertion of olefins in Pd-allyl complexes probably takes place directly from the eta(3)-allyl species. The presence of a phosphane ligand in the reagents plays the role of enhancing the electron density on the Pd atom; this makes the alkene moiety more reactive towards insertion by back-donation from the metal. The results also indicate that the configuration of the new stereogenic centers is fixed in the insertion of the alkene into the (eta(3)-allyl)palladium species. |
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Keywords: | allylation carbocycles density functional calculations insertion palladium |
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