Synthetic Studies Towards the Spiroindimicins

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dc.contributor.advisor Sperry, J en
dc.contributor.author Blair, Lachlan en
dc.date.accessioned 2016-06-15T00:08:07Z en
dc.date.issued 2016 en
dc.identifier.citation 2016 en
dc.identifier.uri http://hdl.handle.net/2292/29074 en
dc.description.abstract This thesis describes synthetic efforts towards the spiroindimicins (135-138), a family of deep sea-derived natural products, which culminated in the total syntheses of (±)-spiroindimicins B (136) and C (137). Our initial efforts sought to construct all members of the family by conducting a dearomative spirocyclization of halogenated bisindolylethanes 237/250 or 267. Ultimately, these attempts were unsuccessful, and neither the [5,6]- (249) or [5,5]- (266) spirobisindole frameworks were accessible using this methodology. In a second approach we examined the use of a Fischer indolization strategy that would construct the spirobisindole frameworks 249 and 260 from aldehydes 291 and 295, respectively. Unfortunately this strategy failed, and resulted in the unexpected side-products 292, 299, and 300. Finally, a revised approach to construct the [5,5]-spirobisindole frameworks present in spiroindimicins B-D was examined, which featured an intramolecular Heck reaction of 422 followed by Fischer indolization of 425 to furnish the [5,5]-spirobisindole 426. Upon the success of this strategy, the ketone 419 was converted to vinyl sulfone 442, which served as the precursor for a Schöllkopf-Magnus-Barton-Zard (SMBZ) reaction to install the pyrrole 445 and hence secure the entire natural product framework. Deprotection steps gave (±)- spiroindimicin C (137) which upon methylation gave (±)-spiroindimicin B (136). Efforts made towards spiroindimicin D using this methodology are also described. en
dc.publisher ResearchSpace@Auckland en
dc.relation.ispartof PhD Thesis - University of Auckland en
dc.relation.isreferencedby UoA99264865410702091 en
dc.rights Items in ResearchSpace are protected by copyright, with all rights reserved, unless otherwise indicated. Previously published items are made available in accordance with the copyright policy of the publisher. en
dc.rights.uri https://researchspace.auckland.ac.nz/docs/uoa-docs/rights.htm en
dc.rights.uri http://creativecommons.org/licenses/by-nc-sa/3.0/nz/ en
dc.title Synthetic Studies Towards the Spiroindimicins en
dc.type Thesis en
thesis.degree.discipline Chemistry en
thesis.degree.grantor The University of Auckland en
thesis.degree.level Doctoral en
thesis.degree.name PhD en
dc.rights.holder Copyright: The Author en
dc.rights.accessrights http://purl.org/eprint/accessRights/OpenAccess en
pubs.elements-id 530752 en
pubs.org-id Science en
pubs.org-id Chemistry en
pubs.record-created-at-source-date 2016-06-15 en


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http://creativecommons.org/licenses/by-nc-sa/3.0/nz/ Except where otherwise noted, this item's license is described as http://creativecommons.org/licenses/by-nc-sa/3.0/nz/

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