Screening of modular phosphoroamidite, siphosphoroamidite and phosphoroamidite ligand libraries in asymmetric metal-catalyzed reactions

Identifier:  TDX:880

Handle: https://hdl.handle.net/20.500.11797/TDX880

Authors:  Raluy González, Eva

Abstract:
One of the main methods for producing enantiomerically pure compounds is metal asymmetric catalysis. An important step in this strategy is the design and preparation of chiral ligands. Among them, new chiral ligands derived from carbohydrate are presented. These ligands are applied to four asymmetric catalytic reactions: Asymmetric Pd-catalyzed allylic substitution, Asymmetric Cu-catalyzed allylic alkylation, Asymmetric Cu-catalyzed 1,4-conjugate addition and Asymmetric Ni-catalyzed 1,2-addition. Chapter 3. Asymmetric Pd-catalyzed allylic substitution. This chapter contains two sections on the development and application of new phosphite-phosphoroamidite and diphosphoroamidite ligand libraries in the asymmetric Pd-catalyzed allylic substitution reactions. The first section describes the synthesis and application of a phosphitephosphoroamidite ligand library in the asymmetric Pd-catalyzed allylic substitution of several substrates with different electronic and steric properties. This chapter also discusses the synthesis and characterization of the Pd-π-allyl intermediates to provide greater insight into the origin of the enantioselectivity. The second section includes the development and application of a new diphosphoroamidite ligand library in asymmetric allylic substitution. Chapter 4. Asymmetric Cu-catalyzed allylic alkylation. This chapter contains one section, which discusses the preliminary results in the application of phosphite-phosphoroamidite, diphosphoroamidite (both ligand libraries developed in Chapter 3) and monophosphororamidite ligands in the asymmetric Cu-catalyzed allylic alkylation reactions. It also describes the synthesis of a new monophosphoroamidite ligand library. Chapter 5. Asymmetric Cu-catalyzed 1,4-conjugate addition. This chapter contains two sections on the application of the phosphite-phosphoroamidite and diphosphoroamidite (developed in Chapter 3), and monophosphoroamidite (developed in Chapter 4) and phosphite ligand libraries in the asymmetric Cu-catalyzed 1,4-addition reactions. The first one reports the investigations of the Cu-catalyzed 1,4-conjugate addition of organometallic reagents to enones using the phosphite-phosphoroamidite and diphosphoroamidite ligand libraries. The second section includes the application of the monophosphoroamidite and monophosphite ligand libraries in the Cu-catalyzed 1,4-conjugate addition of organometallic reagents to cyclic and linear enones. Chapter 6. Asymmetric Ni-catalyzed 1,2-addition. This chapter contains two sections on the application of the phosphite-phosphoroamidite and diphosphoroamidite (developed in Chapter 3) and monophosphoroamidite (developed in Chapter 4) ligand libraries in the asymmetric Ni-catalyzed 1,2-addition reactions. The first one reports the investigations of the Ni-catalyzed trialkylaluminium 1,2-addition to aldehydes using the phosphitephosphoroamidite and diphosphoroamidite ligand libraries. The second section includes the application of the carbohydrate-based monophosphoroamidite ligand library in the Nicatalyzed trialkylaluminium 1,2-addition to several aldehydes types.