Reacciones de formación de enlaces C-C y C-N catalizadas por complejos de cobre y oro

Abstract

This PhD Thesis describes the synthesis and characterization as well as the catalytic activity of copper(I) and gold(I) complexes with tris(pyrazolylmethyl)amine, tris(pyrazolyl)borate and N-heterocyclic carbenes ligands in C-C and C-N bonds forming reactions. This Thesis is divided in four Chapters. The first one describes the preparation and structural characterization of new copper(l) complexes with tris(pyrazolylmethyl)amine (Tpax) ligands and their catalytic activities in the insertion reactions of carbene and nitrene moieties to saturated and unsaturated molecules. The catalytic activity observed with these new complexes is compared to that previously observed with copper(I) complexes with tridentate nitrogen ligands, such as tris(pyrazolyl)borate (Tpx) and tris(pyrazolyl)methane (Tpmx). In the second Chapter, the C-H bond functionalization of indole derivatives with ethyl diazoacetate employing TpxCu(NCMe) complexes as catalysts is described. Additionally, as the reaction takes place through a cyclopropyl indole intermediate, the double functionalization of C2 and C3 positions has consecutively been achieved. The last part of this chapter is devoted to mechanistic studies of this reaction. The third Chapter describes the synthesis and characterization of novel fluorinated imidazolium salts precursors of NHC ligands. Additionally, the preparation of the corresponding copper(I) and gold(I) complexes using these ligands has been carried out. Furthermore, these new gold(l) complexes with fluorinated NHC ligands are used as catalysts in the methane functionalization with ethyl diazoacetate employing scC02 as reaction solvent. The last Chapter studies the catalytic capabilities of NHC-Au(I) complexes in the Mannich addition reactions of 1,3-dicarbonyl compounds with N-protected imines. This Chapter has been written in English to accomplish with the regulation at the University of Huelva to achieve the International Doctorate degree.