A new method for the synthesis of naphthalenes has been recently discovered. The Atom Transfer Radical Cyclisation (ATRC) of diverse 2-allylphenyl2',2',2'-trichloroacetates in the presence of a Cu complex afford schloronaphthalenes in good yields using either microwave or thermolytic methods of activation. A mechanism for the benzannulation reaction is proposed and experiments presented in order to validate this hypothesis. The use of 1,3-bis(2,6-diisopropylphenyl)imidazolium copper(I) chloride [(IPr)CuCl)] along with other metal carbenes is compared to the already reported CuCl/ligand system. Since the scope and synthetic utility of this new benzannulation reaction is restricted due to the use of the MW reactor, a solvent in which the thermal reaction can take place is reported, proving its efficiency in the synthesis of a range of substituted naphthalenes. The potential and versatility of the benzannulation reaction has been investigated. Studies towards the synthesis of gilvocarcin M which contains a tetracyclicaromatic core are presented. Gilvocarcins have potential use as anti-cancer agents and represent a member of the C-aryl glycosides found in natural products. Gilvocarcin M is a challenging target because there are a sparse number of total syntheses reported in the literature. The ATRC reaction of (vinyl)phenyl trichloroacetate has also been investigated, affording the synthesis of functionalised coumarins. The mechanism of this reaction has also been investigated, establishing that, in some cases, aretro-Kharasch reaction is observed.
| Identifer | oai:union.ndltd.org:bl.uk/oai:ethos.bl.uk:527196 |
| Date | January 2010 |
| Creators | Lujan Barroso, Cristina |
| Contributors | Quayle, Peter |
| Publisher | University of Manchester |
| Source Sets | Ethos UK |
| Detected Language | English |
| Type | Electronic Thesis or Dissertation |
| Source | https://www.research.manchester.ac.uk/portal/en/theses/atom-transfer-radical-cyclisation-reactions-in-organic-synthesis(5762bcb7-0c05-4933-b785-1edd68ecb00a).html |
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