Recent Advances in Tandem Reductive Processes

  • Ben Hartley

Student thesis: Doctoral ThesisPhD

Abstract

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 Award5 May 2009
LanguageEnglish
Awarding Institution
  • University of Bath
SupervisorChristopher Frost (Supervisor)

Keywords

  • meldrum's acid
  • Reduction
  • aldehydes
  • reductive dieckmann

Cite this

Recent Advances in Tandem Reductive Processes
Hartley, B. (Author). 5 May 2009

Student thesis: Doctoral ThesisPhD