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Metal-oxo and metal-carbene reagents : applications in the synthesis of natural products and related structures

Metal-oxo and metal-carbene reagents : applications in the synthesis of natural products and related structures
Metal-oxo and metal-carbene reagents : applications in the synthesis of natural products and related structures

The Annonaceous acetogenin cis-sylvaticin (3.12) displays potent antitumour activity. Using permanganate-promoted oxidative cyclisation of 1,5-dienes we have synthesised the C3-17 and C18-34 fragments 4.32 and 4.12 and coupled them by a tethered ring-closing metathesis to provide the cis-sylvaticin backbone with the correct stereochemical configuration.

(-)-Galanthamine (5.1) is a naturally occurring alkaloid used in the treatment of Alzheimer’s disease. We have attempted to synthesise galanthamine by two routes. The first strategy was based on the cyclopropanation of a diazoacetamide of type 5.56 followed by rearrangement to construct the tetracyclic core. The second strategy was based on the intramolecular nucleophilic addition/migration of azide 6.21. Neither route was successful and reasons for this are discussed.

The key step in a recent series of synthesis of endo, exo-formation lignans is a highly diastereoselective C-H insertion. A study was undertaken with the aim of advancing our understanding of the process. This involved the synthesis of five analogues of the diazolactone C-H insertion precursors 7.43a-e, followed by diazo decomposition under various conditions. This investigation has increased our knowledge of the reaction.

University of Southampton
Kemp, Stephen Charles
a32dfdac-92c2-43bd-8245-f2534d21f2ac
Kemp, Stephen Charles
a32dfdac-92c2-43bd-8245-f2534d21f2ac

Kemp, Stephen Charles (2006) Metal-oxo and metal-carbene reagents : applications in the synthesis of natural products and related structures. University of Southampton, Doctoral Thesis.

Record type: Thesis (Doctoral)

Abstract

The Annonaceous acetogenin cis-sylvaticin (3.12) displays potent antitumour activity. Using permanganate-promoted oxidative cyclisation of 1,5-dienes we have synthesised the C3-17 and C18-34 fragments 4.32 and 4.12 and coupled them by a tethered ring-closing metathesis to provide the cis-sylvaticin backbone with the correct stereochemical configuration.

(-)-Galanthamine (5.1) is a naturally occurring alkaloid used in the treatment of Alzheimer’s disease. We have attempted to synthesise galanthamine by two routes. The first strategy was based on the cyclopropanation of a diazoacetamide of type 5.56 followed by rearrangement to construct the tetracyclic core. The second strategy was based on the intramolecular nucleophilic addition/migration of azide 6.21. Neither route was successful and reasons for this are discussed.

The key step in a recent series of synthesis of endo, exo-formation lignans is a highly diastereoselective C-H insertion. A study was undertaken with the aim of advancing our understanding of the process. This involved the synthesis of five analogues of the diazolactone C-H insertion precursors 7.43a-e, followed by diazo decomposition under various conditions. This investigation has increased our knowledge of the reaction.

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Published date: 2006

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Local EPrints ID: 466184
URI: http://eprints.soton.ac.uk/id/eprint/466184
PURE UUID: dc56dc54-c1cf-4f4f-87be-14bf082f75e8

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Date deposited: 05 Jul 2022 04:41
Last modified: 16 Mar 2024 20:33

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Author: Stephen Charles Kemp

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