I. Copper catalyzed asymmetric transformations II. Copper-in-charcoal catalyzed Ullmann etherification III. Toward the asymmetric syntheses of 3,3'-substituted cyclo-NOBIN ligands

Transition metal-catalyzed asymmetric transformations have become an essential part of contemporary organic synthesis. As the majority of pharmaceuticals today contain at least one chiral center, demand has dictated the need for better and more efficient stereoselective methods. Copper hydride-catalyzed hydrosilylation has become a well-developed method for the asymmetric reduction of various carbonyls and activated olefins. Paired with the right nonracemic ligand, this catalyst can afford nearly enantiopure reduction products in generally high yields. Nevertheless, such transformations are sometimes limited by lengthy reaction times and the necessity for hazardous organic solvents as reaction media. Methods that increase rates of reduction through the judicious application of heat have been developed. Also, the efficacy of aqueous-based copper hydride catalysis is currently being investigated. Furthermore, a highly stereoselective intramolecular tandem reduction-aldol reaction has been developed to demonstrate the capability and expand the scope of asymmetric copper hydride catalysis.;As industry continues to search for economical and environmentally friendly means of catalysis, many heterogeneous catalysts have been produced that allow metals to be recycled while limiting the production of hazardous waste. The heterogeneous catalyst copper-in-charcoal (Cu/C) was developed with those goals in mind. Catalytic Cu/C was applied to the coupling of aryl bromides and aryl alcohols to form various Ullmann-type diaryl ethers. Although copper bleeding was initially observed, the reaction conditions were optimized to maintain the overall heterogeneity of the catalyst and allow for its reuse.;Nonracemic ligands that are capable of effecting a high degree of stereoinduction are in a constant state of development. The biaryl ligand array is specifically dynamic. Many catalytically viable 3,3'-substituted BINAP, BINOL, and BINAM ligands have been constructed for specific transformations. However, the difficulty in synthesizing such scaffolds has dictated a general unavailability and/or a high cost. Alternatively, nonracemic binaphthyl ligands have been constructed using a modular approach that employs the influence of a chiral tether. The approach was applied toward the syntheses of 3 or 3'-substituted cyclo-NOBIN ligands.