This thesis describes the total synthesis of (-)-blepharocalyxin D and related analogues via a novel Prins-type cyclisation that allows the core bicyclic stlUcture to be synthesised in a single step, generating both rings and four new stereocenters. A variety of synthetic routes to y,8-unsaturated alcohols such as 305 were investigated, the key steps in the final route including Wittig olefination, rhodium catalysed 1,4-addition and Chugaev elimination to give 305 which was taken fOlward in the synthesis of 35. In the final chapter, further y,8-unsaturated alcohols were prepared and used in the synthesis of bicyclic lactone 329. Alkene 328 was modified post cyclisation to give a series of novel compounds including protected amine 345. It was found that the reaction of y,8-unsaturated alcohol 106 with aldehydes gave trisubstituted tetrahydropyrans with good stereocontrol. By varying the reaction conditions either an axial or equatorial side-chain was introduced at C-3.
| Identifer | oai:union.ndltd.org:bl.uk/oai:ethos.bl.uk:664976 |
| Date | January 2014 |
| Creators | Cons, Benjamin David |
| Publisher | University of Bristol |
| Source Sets | Ethos UK |
| Detected Language | English |
| Type | Electronic Thesis or Dissertation |
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