Gold (i)-catalyzed cyclizations of 1,6- and 1,7-enynes: new gold complexes and cyclopropanation reactions

Identificador:  TDX:813

Handle: https://hdl.handle.net/20.500.11797/TDX813

Autors:  Herrero Gómez, Elena

Resum:
In this PhD thesis we have studied different experimental and theoretical aspects of the gold(I)-catalyzed cyclization of enynes. The work has been divided in two chapters, one related with the study of gold(I) complexes and the second one focused on the applications of gold complexes for the activation of alkynes, more precisely on the enyne cyclization reaction.Firstly, we have performed a computational study of a family of group 11 metal complexes as well as the synthesis and structural characterization of the first gold(I) cationic complexes displaying η1−η2 gold(I)-arene interactions. We have also synthesized a phosphite gold(I) complex which is the most active catalyst for enyne cycloisomerizations.On the other hand, the intermolecular trapping of the carbene intermediates involved in the gold(I)-catalyzed cyclization of 1,6-enynes with olefins was achieved, giving rise to one of the few examples of gold(I)-catalyzed cyclopropanations. We have also performed a computacional study of the gold(I)-catalyzed cyclization of 1,7-enynes and broadened the scope of the gold(I)-catalyzed [4+2] cycloaddition by its successful application to substituted 1,7-enynes.