Enantioselective transformations of α-diazocarbonyl compounds; catalyst and substrate effects

Abstract

The primary objective of this thesis was an extensive investigation into transition metal catalysed intramolecular C–H insertion reactions of α-diazoacetamides and intramolecular aromatic addition reactions of α-diazoketones. Exploration of the effect of substrate structure and the impact of various aspects of the catalyst complex was undertaken to determine which has a greater influence on the ensuing C–H insertion and aromatic addition reactions. While particular attention was paid to copper-bisoxazoline catalyst complexes, studies were also conducted, although to a lesser extent, using the more widely studied achiral and chiral rhodium catalysts. Significantly, use of the copper complexes in C–H insertion reactions of α-diazoacetamides resulted in formation of γ-lactams and β-lactams in high enantiopurities, 91% ee and 83% ee, while copper catalysed aromatic addition reactions resulted in formation of azulenones in up to 92% ee.