Synthetic and biosynthetic studies of the brevianamides
| dc.contributor.author | Halligan, Kathleen Marie, author | |
| dc.contributor.author | Williams, Robert M., advisor | |
| dc.date.accessioned | 2022-11-28T17:46:41Z | |
| dc.date.available | 2022-11-28T17:46:41Z | |
| dc.date.issued | 2000 | |
| dc.description.abstract | The preparation of a pinacol-type rearrangement precursor towards the total synthesis of target indoxyl 8 is presented. The route contains three key steps. These include a photooxidation reaction that installs a hydroxy group in the required stereospecific position, a pinacol-type rearrangement to provide the indoxyl core structure and a Strecker reaction to extend the carbon chain to the aminonitrile derivative. Though several other routes to hydroxyindolenines were pursued, this particular pathway shows the most promise for the completion of indoxyl 8 since the crucial pinacol rearrangement was successful. This route is also amenable to 13C-labeled synthesis of indoxyl 8 and azadiene 29. The biomimetic synthesis of brevianamide B is described. Brevianamide B and epibrevianamide A were synthesized from deoxybrevianamide E in six steps. A Diels-Alder precursor was formed via oxidation of the diketopiperazine moiety and praline ring followed by rearrangement to the azadiene. A [4 + 2] cycloaddition reaction took place to provide two hexacyclic adducts. Oxidation at the 3-position of the indole supplied the hydroxyindolenines. A pinacol-type rearrangement of the respective hydroxy derivatives furnished brevianamide B and epibrevianamide A. | |
| dc.format.medium | doctoral dissertations | |
| dc.identifier.uri | https://hdl.handle.net/10217/235845 | |
| dc.language | English | |
| dc.language.iso | eng | |
| dc.publisher | Colorado State University. Libraries | |
| dc.relation | Catalog record number (MMS ID): 991009205909703361 | |
| dc.relation | QP517.B57H35 2000 | |
| dc.relation.ispartof | 2000-2019 | |
| dc.rights | Copyright and other restrictions may apply. User is responsible for compliance with all applicable laws. For information about copyright law, please see https://libguides.colostate.edu/copyright. | |
| dc.subject | Metabolites | |
| dc.subject | Biosynthesis | |
| dc.subject | Diels-Alder reaction | |
| dc.title | Synthetic and biosynthetic studies of the brevianamides | |
| dc.type | Text | |
| dcterms.rights.dpla | This Item is protected by copyright and/or related rights (https://rightsstatements.org/vocab/InC/1.0/). You are free to use this Item in any way that is permitted by the copyright and related rights legislation that applies to your use. For other uses you need to obtain permission from the rights-holder(s). | |
| thesis.degree.discipline | Chemistry | |
| thesis.degree.grantor | Colorado State University | |
| thesis.degree.level | Doctoral | |
| thesis.degree.name | Doctor of Philosophy (Ph.D.) |
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