This thesis describes the development of new methods towards the stereoselective synthesis of oxazolidinones and [3,3] sigmatropic rearrangements to allylamines from allylic carbamate starting materials. Unlike previous protocols found in the literature the oxazolidinones formed do not have a protected nitrogen atom. The stereoselective formation of chlorohydroxylated products is demonstrated with the view to utilise this reaction as part of an alternative to the tethered aminohydroxylation. A novel diastereoselective iodine mediated cyclisation of allylic carbamates and allylic ureas to oxazolidinones and imidazolidinones respectively is described. The reaction has also been telescoped from an aldehyde completing three reactions in a one pot environment. The use of palladium (II) catalysis for oxazolidinone formation is also shown in an attempt to devise an enantioselective reaction analogous to the highly acclaimed tethered aminohydroxylation. Palladium (II) catalysis is also utilised for the diastereoselective conversion of allylic carbamates to allylic amines. Chapter 1: An overview to the uses of osmium and palladium in the activation of alkenes described in the literature. Chapter 2: Highlights our research into the formation of oxazolidinone rings from and [3,3] sigmatropic rearrangements of allylic carbamates. Chapter 3: Provides experimental data for our studies.
| Identifer | oai:union.ndltd.org:bl.uk/oai:ethos.bl.uk:487767 |
| Date | January 2007 |
| Creators | Warrington, Adam David |
| Publisher | Loughborough University |
| Source Sets | Ethos UK |
| Detected Language | English |
| Type | Electronic Thesis or Dissertation |
| Source | https://dspace.lboro.ac.uk/2134/33674 |
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