Identificador: TDX:4272
Autors: García Padilla, Eduardo
Resum:
This Doctoral Thesis explores gold(I) catalysis. Addressing gaps in understanding unusual reactivity patterns, regio- and
stereoselectivity shifts, selective transformations, and bimetallic systems, the thesis investigates these reactions both
experimentally and computationally. In the manuscript are presented examples of reactivity guided by the computational
insight. The research uncovers the intermediates in 1,5-enynes and 1,5-allenenes, including tautomeric
cyclopropylcarbene and vinylgold species, along with non-classical carbocationic species. Computational analysis
sheds light on their bonding. Mechanistic insights are extended to single- and double-cleavage enyne rearrangements,
explaining factors behind stereoconvergence, exocyclic or endocyclic selectivity, and single or double cleavage.
Additionally, a study of enyne cyclizations and alkoxycyclizations explores the role of alcohol in the enantioselectivity of
the reaction. The 1,3,5-selective cyclotrimerization of alkynes is studied, offering computational and experimental
support for gold(I) eta1-cyclobutadiene and Dewar benzene intermediates. This leads to the development of
intramolecular cyclotrimerizations, yielding formal 1,2,3-cyclotrimerized products. Furthermore, a ligand platform for
gold(I) bimetallic complexes is designed, synthesized, and characterized. These complexes are explored for reactivity,
with combined computational and experimental work shedding light on the coordination chemistry and catalysis of
cyclometallated complexes and self-activating catalysis with [AuAu] complexes.
Repositori URV