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

Identifier:  TDX:829

Handle: https://hdl.handle.net/20.500.11797/TDX829

Authors:  Pérez Galán, Patricia

Abstract:
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. <br/>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. <br/>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. <br/>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.