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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
1

Solving the mechanistic puzzle of gold-catalyzed cyclization of 1,6-enynes and beyond

Pérez Galán, Patricia 25 March 2010 (has links)
La tesis se centra en el estudio del mecanismo de las reacciones de cicloisomerización de 1,6-eninos catalizada por complejos de oro(I). Evidencia experimental de la existencia de los intermedios propuestos se ha obtenido mediante la reacción de atrapamiento intermolecular de dichos intermedios, con alquenos, mediante la reacción de bisciclopropanación, y también por adición externa de nucleófilos. Por otra parte, la reacción de cicloadición [4 + 2] de aril eninos sustituidos fue estudiada. Esta reacción se ha utilizado como metodología clave para la síntesis de productos naturales como la familia de las picnanthuquinonas, También se ha estudiado el mecanismo de trasposición por rututa de enlace simple o doble y la formación de ciclobutenos en la reacción de 1,6-eninos aril substituidos. / This Thesis is focused on the mechanism of the cycloisomerization reaction of 1,6-enyes catalyzed by gold(I) complexes. We obtained experimental evidence for the existence of the proposed intermediates by intermolecular trapping with alkenes, through a biscyclopropanation reaction and by reaction with external nucleophiles. On the other hand, the [4 + 2] cycloaddition reaction of substituted aryl enynes was studied. This reaction was used in an approach for the total synthesis of natural products such as the pycnanthuquinones. We have also studied the mechanism of the simple/double cleavage rearrangement and the formation of cyclobutenes in the reaction of aryl substituted 1,6-enynes. Moreover, new silver and copper complexes were prepared and structurally characterized. The new complexes were assayed in the cycloisomerization and cyclopropanation reactions. Metal-arene interactions were also studied.

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