Screening of Modular Carbohydrate Ligand Libraries in Asymmetric Metal-catalyzed C-C and C-X Bond Formation Reactions

Identifier:  TDX:868

Handle: https://hdl.handle.net/20.500.11797/TDX868

Authors:  Mata Campaña, Yvette Angela

Abstract:
The growing demand for enantiomerically pure compounds for the development of pharmaceuticals, agrochemicals and flavors has captured the interest of the chemist in the last few decades. Of the various methods for producing enantiopure compounds, enantioselective homogeneous metal catalysis is an attractive one. In this context, carbohydrates have many advantages: they are readily available, are highly functionalized and have several stereogenic centers. This enables series of chiral ligands to be synthesized and screened in the search for high activities and selectivities for each particular reaction. In this context, this thesis focuses on the development of new chiral ligand libraries derived from carbohydrates, the synthesis of new catalyst precursors and their application in the Pd-catalyzed asymmetric allylic substitution, Pd-catalyzed asymmetric Heck reactions, Ni-catalyzed asymmetric addition of trialkylaluminium to aldehydes, and Cu-catalyzed asymmetric 1,4-conjugated addition of trialkylaluminium reagents to enones. For this porpose, we have designed and syntezied 3 new sugar based ligand libraries: phosphite-oxazoline (L1-L5), phosphite-phosphoroamidite (L6) i monophosphite (L7-L11) (Figure 1). After introduction (Chapter 1) and objectives (Chapter 2), in chapter 3 is discussed the synthesis and characterization of the ligand libraries (L1-L11) and and their application in the asymetric Pd-catalyzed allylic substituion reactions. Using phosphite-oxazoline ligands (L1-L5) we observed important effects of the oxazoline substituents and the axial chirality and the substituents of the biaryl moieties. However, the effects of these parameters depended on each substrate. High enantioselectivities (up to 99%) and good activities have been achieved