| The objective of this thesis research is to develop practically useful chirotechnology for the production of optically pure compounds. Several approaches were taken, including design of highly enantioselective homogeneous asymmetric catalysts and their immobilization in room-temperature ionic liquids (RTILs) and synthesis of chiral porous solids for heterogeneous asymmetric catalysis and chiral separations.; Chapter 1 covers the fundamentals of chirality and introduces several common methods for the production of chiral compounds. A particular emphasis has been placed on the fundamental concepts of asymmetric catalysis, as illustrated by asymmetric epoxidation, Diels-Alder reaction, addition of alkyl reagents, and reductions.; Chapter 2 discusses the design strategies, synthesis, characterization, and applications of porous solids. Traditional porous inorganic solids such as zeolites and molecular sieves were first discussed, followed by an overview of porous metal-organic coordination networks.; Chapter 3 presents the synthesis and characterization of homochiral porous metal-carboxylate coordination networks. Several coordination networks and cages were assembled using two atropisomeric dicarboxylate bridging ligands. Extensive characterization of these solids was also presented.; Chapter 4 describes the first porous lamellar lanthanide bisphosphonates that are pillared with chiral crown ethers. Relevance of this model system to the design of media for bulk chiral separations is discussed.; Chapter 5 presents the synthesis and applications of chiral porous zirconium phosphonates in heterogeneous asymmetric catalysis. These chiral porous solids were synthesized via a molecular building block approach, and examined for catalytic applications in additions of diethylzinc to aldehydes and asymmetric hydrogenation of beta-keto esters and aromatic ketones.; Chapter 6 discusses the development of a family of tunable chiral diphosphines based on the BINAP framework and their applications in highly enantioselective hydrogenation of aromatic ketones. The most stereoselective hydrogenation catalysts were developed in this research.; Chapter 7 describes the immobilization of homogeneous asymmetric catalysts in RTILs. Asymmetric hydrogenation reactions of beta-alkyl ketoesters, beta-aryl ketoesters, and aromatic ketones have been carried out in RTILs with very high enantioselectivity. Asymmetric catalysts have been effectively immobilized in RTILs. |
