• Epimeric L-Proline Derived Imidazolone Chiral Auxiliaries for the Stereoselective Alkylative Birch Reduction of Aromatic Esters and Benzonitriles

      Cadwallader, Dusty; Department of Chemistry
      Described in this thesis are several advancements of imidazolidinone chiral auxiliaries. Initially, attempts were made to develop a N-heterocyclic carbene ligand derived from the N-benzyl analog of the auxiliary. Attempts to design a monodentate ligand as well as a bidentate ligand bearing an alcohol side chain were both shown to be unsuccessful. Work on the N-phenyl variant of the auxiliary included expanding upon our recently discovered methodology; a Birch reduction alkylation sequence of an aromatic ester yielding chiral quaternary carbon centres in a stereoselective matter. In substrates that demonstrate poor stereoselectivity, modification of the auxiliary to include a larger neopentoxy directing group gives way to increased selectivity. This work also includes the same Birch reduction alkylation sequence on a series of benzonitrile substrates with up to 64:36 diastereomeric ratio from either epimer of the auxiliary. The low selectivity of the benzonitrile substrates is offset by the resulting diastereomers of the dihydrobenzonitrile products being chromatographically separable. This results in the first preparation of optically pure quaternary carbons alpha to nitrile by Birch-type reductive alkylation. Progress was also made in the manipulation of chiral auxiliaries bearing the chiral alkoxy moiety. These functional groups were transformed into hemiaminals by citric acid hydrolysis in a 3:2 ratio with imidazolone by-products formed by acid mediated elimination of alcohol.