Design, Synthesis Of Chiral Tertiary Amine-Thiourea Catalysts Derived From Both α-Amino Acids And Carbohydrates, And Their Application In Asymmetric Conjugate Addition Reactions

The utilization of hydrogen bonding as an activation force has become a powerful tool in asymmetric organocatalysis. Since Takemoto in 2003 reported the first class of chiral bifunctional tertiary amine-thiourea organocatalysts which catalyzed highly enantioselective Michael reaction of malonates with nitroolefins, remarkable advance has been made in the tertiary amine-thiourea-catalyzed asymmetric transformations. In this context, the development of new types of chiral bifunctional tertiary amine-thiourea organocatalysts has become a focal point of attention.This thesis cludes three parts.In the first part, the progress on the organocatalytic asymmetric reactions catalyzed by chiral bisfunctional thiourea-tertiary amine thioureas is summarized.In the second part, eleven chiral bifunctional tertiary amine-thiourea catalysts derived from both acyclicα-amino acids and carbohydrates have been designed and synthesized.In the third part, the application of newly designed chiral bifunctional tertiary amine-thiourea catalysts to the direct enantioselective conjugate addition of acetyl- acetonate to nitroolefins has been investigated. These bifunctional thiourea organo- catalysts promoted the enantioselective conjugate addition of acetylacetone to various nitroolefins in good yields (up to 93%) with good enantioselectivity (up to 91% ee). The research demonstrates the advantages of incorporating two stereocontrolling structures into a single catalyst. Futhermore, doubly stereocontrolled catalytic conjugate addition of acetylacetone with nitroolefins has been achieved.