Towards the total synthesis of hypoestoxide and dihypoestoxide
The involvement of hetero Diels-Alder dimerisations in the biosynthesis of natural products has been a source of debate for many years. Hypoestoxide and dihypoestoxide are two verticillane-type diterpenoids with closely related structures. Both were isolated from the same extracts of Hypoestes rosea...
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| Format: | Thesis (University of Nottingham only) |
| Language: | English |
| Published: |
2017
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| Online Access: | https://eprints.nottingham.ac.uk/41908/ |
| Summary: | The involvement of hetero Diels-Alder dimerisations in the biosynthesis of natural products has been a source of debate for many years. Hypoestoxide and dihypoestoxide are two verticillane-type diterpenoids with closely related structures. Both were isolated from the same extracts of Hypoestes rosea in Nigeria. These two natural products constitute another example of a potential hetero Diels-Alder dimerisation in biosynthesis. Therefore, this thesis reports the work towards the diterpene hypoestoxide in order to study the hetero Diels-Alder dimerisation.
The introduction emphasises the different biological properties of hypoestoxide and the isolation of dihypoestoxide. The biosynthesis of terpenes, the only previous synthesis of an isomer of hypoestoxide reported to date and the hetero Diels-Alder dimerisation in biosynthesis are described. Former Hayes group work about the stereochemical assignment of dihypoestoxide is also detailed in this part.
The results and discussion suggests a synthetic route to hypoestoxide starting from geraniol, which constitutes a sustainable source of starting material for this synthesis. Different approaches towards the formation of the exocyclic enone moiety of hypoestoxide at a later stage in the synthesis would be discussed. Challenges to remove the additional carbon at C12 position would be detailed in this part. A brief conclusion and future work in this regard are given.
Experimental procedures and full characterisation data of the different intermediates synthesised by this route are detailed. |
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