The research presented herein is concerned with the exploration of tandem processes initiated by the conjugate reduction of Michael acceptors, encompassing the asymmetric reductive Dieckmann reaction and the two-carbon homologation of aldehydes by two complementary methodologies.
Chapter 1 introduces the area of transition metal catalysed tandem reductive processes as a tool for carbon-carbon bond formation. An extensive discussion of this methodology is included and recent advances in the area are highlighted.
Chapter 2 discusses the initial study into the asymmetric reductive Dieckmann condensation. 3,3’-Disubstituted 4-oxopyrrolidines were synthesised in up to 93% ee using both molybdenum and copper catalysis.
Chapter 3 describes the novel molybdenum-catalysed two-carbon homologation of aldehydes by the reduction of alkylidene Meldrum’s acid derivatives. No over reduction to the corresponding alcohol is observed, as the aldehyde functionality remains protected until hydrolysis.
Chapter 4 discusses the mild, expeditious amine promoted reduction of cyclic malonates to β-substituted propionaldehydes. The synthetic utility of the methodology is demonstrated by the synthesis of γ-substituted propylamines in a one-pot hydrosilylation/reductive amination process.
Chapter 5 describes the synthesis and characterisation for the compounds discussed in chapters 2, 3 and 4.
|Date of Award||5 May 2009|
|Supervisor||Christopher Frost (Supervisor)|
- meldrum's acid
- reductive dieckmann