Experimental and Computational Studies on Copper and Hydrobenzoin Derivatives in Catalytic Asymmetric Reactions

The use of theory to understand and facilitate catalytic enantioselective organic transformations involving copper and hydrobenzoin derivatives is reported. Section A details the use of theory to predict, facilitate, and understand a copper promoted amino oxygenation reaction reported by Chemler et al. Using Density Functional Theory (DFT), employing the hybrid B3LYP functional and a LanL2DZ/6-31G(d) basis set, the mechanistic details were studied on a N-tosyl-o-allylaniline and a [alpha]-methyl-[gamma]-alkenyl sulfonamide substrate. The results suggest the N-C bond formation proceeds via a cisaminocupration, and not through a radical-type mechanism. Additionally, the origin of diastereoselection observed with [alpha]-methyl-[gamma]-alkenyl sulfonamide arises from avoidance of unfavourable steric interactions between the methyl substituent and the N -protecting group. Section B details the computationally guided, experimental investigation of two hydrobenzoin derivatives as ligands/ catalysts, as well as the attempted synthesis of a third hydrobenzoin derivative. The bis-boronic acid derived from hydrobenzoin was successful as a Lewis acid catalyst in the Bignielli reaction and the Conia ene reaction, but provided only racemic products. The chiral diol derived from hydrobenzoin successfully increased the rate of the addition of diethyl zinc to benzaldehyde in the presence of titanium tetraisopropoxide, however poor enantioinduction was obseverved. Notably, the observed reactivity was successfully predicted by theoretical calculations.

Investigating the potential of thecamoebians (testate amoebae) as bio-indicators of impact of oil sands mining operations on freshwater environments in Northeastern Alberta, Canada

Thecamoebian (testate amoeba) species diversity and assemblages in reclamation wetlands and lakes in northeastern Alberta respond to chemical and physical parameters associated with oil sands extraction. Ecosystems more impacted by OSPM (oil sands process-affected material) contain sparse, low-diversity populations dominated by centropyxid taxa and Arcella vulgaris. More abundant and diverse thecamoebian populations rich in difflugiid species characterize environments with lower OSPM concentrations. These shelled protists respond quickly to environmental change, allowing year-to-year variations in OSPM impact to be recorded. Their fossil record thus provides corporations with interests in the Athabasca Oil Sands with a potential means of measuring the progression of highlyimpacted aquatic environments to more natural wetlands. Development of this metric required investigation of controls on their fossil assemblage (e.g. seasonal variability, fossilization potential) and their biogeographic distribution, not only in the constructed lakes and wetlands on the oil sands leases, but also in natural environments across Alberta.

Watercolour painting of the Woodruff coat of arms on paper

Watercolour painting of the Woodruff coat of arms on paper. This measures 43 cm. x 31 cm., n.d.