Progress toward the total synthesis of stemocurtisine and asymmetric synthesis of endoperoxide anticancer agents via Brønsted acid cascade catalysis
| dc.contributor.author | Rubush, David Michael, author | |
| dc.contributor.author | Rovis, Tomislav, advisor | |
| dc.contributor.author | Kennan, Alan, committee member | |
| dc.contributor.author | Crans, Debbie, committee member | |
| dc.contributor.author | Chen, Eugene, committee member | |
| dc.contributor.author | Kanatous, Shane, committee member | |
| dc.date.accessioned | 2007-01-03T08:26:24Z | |
| dc.date.available | 2007-01-03T08:26:24Z | |
| dc.date.issued | 2012 | |
| dc.description.abstract | A viable route toward the pyrido-azepine core of stemocurtisine involving an N-heterocyclic carbene catalyzed Stetter reaction has been realized. The key steps involve a formal [3+2] cycloaddition of enones with isocyanoacetates and a catalytic asymmetric intramolecular Stetter reaction. Additionally, a diastereoselective intramolecular Stetter reaction was achieved to access highly substituted pyrrolidines. Asymmetric Brønsted acid catalyzed cascade reactions were also investigated. A diastereoselective acetalization/oxa-Micahel cascade has been developed to provide dioxolanes and oxazolidines using diphenylphosphinic acid as a catalyst. The enantioselective variant of this reaction was explored with minor success. The desymmetrization of p-peroxyquinols using a Brønsted acid catalyzed acetalization/oxa-Michael cascade was achieved in high yields and selectivities for a variety of aliphatic and aryl aldehydes. Mechanistic studies suggest that the reaction proceeds through a dynamic kinetic resolution of the peroxy-hemiacetal intermediate. The resulting 1,2,4-trioxane products were derivatized and show potent cytotoxicity toward specific cancer cells. | |
| dc.format.medium | born digital | |
| dc.format.medium | doctoral dissertations | |
| dc.identifier | Rubush_colostate_0053A_11415.pdf | |
| dc.identifier | ETDF2012500324CHEM | |
| dc.identifier.uri | http://hdl.handle.net/10217/71583 | |
| dc.language | English | |
| dc.language.iso | eng | |
| dc.publisher | Colorado State University. Libraries | |
| 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.title | Progress toward the total synthesis of stemocurtisine and asymmetric synthesis of endoperoxide anticancer agents via Brønsted acid cascade catalysis | |
| 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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