Adventures in natural product chemistry

Halichlorine, pinnaic acid and pinnarine are a novel family of marine alkaloids, characterised by their common 6-aza-spiro[4.5]decane ring system. First isolated in 1996 by Uemura et al, they have been shown to be biologically active with potential applications in the fields of inflammatory response and tumor metastasis. This project details the attempted total synthesis of the halichlorine family, focusing on the construction of the 6-aza-spiro[4.5]decane core ring system from cyclopentanone derivatives. Synthesis of the challenging C-14 and C-13 centers was achived diastereoselectively via Tsuji-Trost allylations. However, attempts to deliver the C-9 spirocyclic centre were met with failure. Exploration of secondary synthetic routes were also largely unsuccessful. Secondary projects detail the attempted N-allylation of sulfinimines, aza-Heck cyclisations for the synthesis of anatoxin-a analogues and Synthetic methodology for the synthesis of renewable monomers from the seed oil derived fatty acid, vernolic acid.