Biomimetic asymmetric catalysis based on biological and synthetic macromolecular scaffolds

Tremendous efforts have been devoted to the design and fabrication of enzyme mimetics based on various macromolecular scaffolds by chemists. These macromolecules can be roughly divided into two groups: biological scaffolds (i.e., proteins, peptides and nucleotides) and synthetic cavities with hydrophobic pockets. Candidates from both families can provide a combination of interactions (e.g., hydrogen bonding, π-π stacking, electrostatic and hydrophobic interactions) to the substrate, the transition state and the metal complex. Thereby, the macromolecular components around the metal center are defined as the second coordination sphere. These comprehensive actions, in some notable examples, brought new reactivities and selectivities to a variety of important organic transformations. This thesis focus on the design of new biomimetic catalytic systems and applied them as asymmetric catalysts for various chemical reactions.