Solvolysis of enantioenriched dihalides and its application to the synthesis of the brominated chamigrene sesquiterpenes
Abstract/Contents
- Abstract
- To date, more than 2,000 natural products have been isolated and structurally characterized which contain either a chlorine- or bromine-bearing stereocenter. Of these secondary metabolites, approximately 500 contain a brominated five-, six-, or seven-membered cyclic scaffold that is often further embedded within a larger terpene-derived polycyclic architecture. Despite the abundance of these motifs in nature, synthetic technologies providing enantioselective access to these structures are largely deficient. To access such structural motifs, we developed a methodology wherein enantioenriched bromochlorides were subjected to ionizing media (hexafluoroisopropanol) to generate a non-racemizing bromonium ion, which could be captured intramolecularly leading to a cyclized product with near-perfect enantiospecificity. This solvolytic bromonium-initiated cyclization was used to access numerous natural product-relevant scaffolds. The analogous enantioenriched dibromides were found to rapidly racemize under these ionizing conditions. This methodology was applied to the synthesis of several brominated chamigrene sesquiterpenes, a class of approximately 100 red algal-derived secondary metabolites. The flagship member of this class, (+)-aplydactone, and its putative biosynthetic precursor, (--)-dactylone, were synthesized enantioselectively for the first time.
Description
| Type of resource | text |
|---|---|
| Form | electronic resource; remote; computer; online resource |
| Extent | 1 online resource. |
| Place | California |
| Place | [Stanford, California] |
| Publisher | [Stanford University] |
| Copyright date | 2018; ©2018 |
| Publication date | 2018; 2018 |
| Issuance | monographic |
| Language | English |
Creators/Contributors
| Author | Burckle, Alexander James |
|---|---|
| Degree supervisor | Burns, Noah |
| Thesis advisor | Burns, Noah |
| Thesis advisor | Du Bois, Justin |
| Thesis advisor | Waymouth, Robert M |
| Degree committee member | Du Bois, Justin |
| Degree committee member | Waymouth, Robert M |
| Associated with | Stanford University, Department of Chemistry. |
Subjects
| Genre | Theses |
|---|---|
| Genre | Text |
Bibliographic information
| Statement of responsibility | Alexander James Burckle. |
|---|---|
| Note | Submitted to the Department of Chemistry. |
| Thesis | Thesis Ph.D. Stanford University 2018. |
| Location | electronic resource |
Access conditions
- Copyright
- © 2018 by Alexander James Burckle
- License
- This work is licensed under a Creative Commons Attribution Non Commercial 3.0 Unported license (CC BY-NC).
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