Development and application of enantioselective H-bond donor organocatalysts

This thesis presents the application and development of H-bond donor organocatalysts. Chapter 2 presents an intramolecular Michael addition of β-dicarbonyls onto α,β-unsaturated esters catalyzed by tertiary amine/H-bond donor bifunctional catalysts, achieving up to 88% ee. Chapter 3 outlines the design and synthesis of a new family of cinchona-derived H-bond donor/ammonium salt phase-transfer catalysts. The ability of these asymmetric phase-transfer catalysts to activate less reactive substrates than their tertiary amine analogues and to induce higher levels of enantiocontrol than commercially available phase-transfer catalysts was demonstrated in an intramolecular Michael addition. Chapter 4 details the highly successful application of these new H-bond donor/ammonium salt phase-transfer catalysts to the enantio- and diastereoselective nitro-Mannich reaction of α-amido sulfones with nitroalkanes. Preliminary investigations into a novel phase-transfer catalyzed asymmetric ketimine reduction demonstrate the ability of these catalysts to provide access to new methods.