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Studies on the biosynthesis of the stephacidins and notoamides. Total synthesis of notoamide S and notoamide T. and Progress toward the synthesis of chrysogenamide A

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dc.contributor.authorMcAfoos, Timothy Jospeh, author
dc.contributor.authorWilliams, Robert M., advisor
dc.contributor.authorKennan, Alan J., committee member
dc.contributor.authorWood, John L., committee member
dc.contributor.authorFinke, Richard G., committee member
dc.contributor.authorCrick, Dean C., committee member
dc.date.accessioned2007-01-03T05:34:44Z
dc.date.available2007-01-03T05:34:44Z
dc.date.issued2011
dc.description.abstractHerein I discuss my efforts toward the elucidation of the biosynthesis of the stephacidins and notoamide family of natural products. Notoamide S has been suggested to be the final common precursor between two different fungal strains, Aspergillus sp. and Aspergillus versicolor, before diverging to form enantiomerically opposite natural products (+) and (-)-stephacidin A and (+) and (-)-notoamide B. The synthesis of notoamide S comes from coupling N-Fmoc proline with a 6-hydroxy-7-prenyl-2-reverse prenyl tryptophan derivative synthesized through a late stage Claisen rearrangement. The oxidation of notoamide S affords an achiral azadiene that leads to an intramolecular Diels-Alder providing a new product, notoamide T, containing the bicyclo[2.2.2]diazaoctane ring system with the 6-hydroxy-7-prenyl indole ring of notoamide S. The synthesis of notoamide T is accomplished through a radical addition to the pyran ring of stephacidin A followed by an elimination ring opening event to provide the 6-hydroxy-7-prenyl indole. Chrysogenamide A is the newest member of the marcfortine family of natural products. Herein I discuss the synthesis of 7-prenyl-2-reverse prenyl indole through a thio-Claisen reaction and subsequent Lewis acid mediated sulfide removal. Coupling of a pipecolic acid derivative with the 7-prenyl-2-reverse prenyl tryptophan leads to the dipeptide containing all of the carbons needed in chrysogenamide A. I propose that chrysogenamide A can be synthesized through an unprecedented intramolecular Diels-Alder reaction of a monoketopiperazine by a condensation/tautomerization event leading to the appropriate azadiene for the intramolecular Diels-Alder reaction. A final oxidation of the intramolecular Diels-Alder product would lead to chrysogenamide A and what could be a newly proposed biosynthesis of a monoketopiperazine.
dc.format.mediumborn digital
dc.format.mediumdoctoral dissertations
dc.identifierMcAfoos_colostate_0053A_10499.pdf
dc.identifier.urihttp://hdl.handle.net/10217/48158
dc.languageEnglish
dc.language.isoeng
dc.publisherColorado State University. Libraries
dc.relation.ispartof2000-2019
dc.rightsCopyright 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.subjectchrysogenamide
dc.subjectstephacidin
dc.subjectnotoamide
dc.titleStudies on the biosynthesis of the stephacidins and notoamides. Total synthesis of notoamide S and notoamide T. and Progress toward the synthesis of chrysogenamide A
dc.title.alternativeTotal synthesis of notoamide S and notoamide T.
dc.title.alternativeProgress toward the synthesis of chrysogenamide A
dc.typeText
dcterms.rights.dplaThis 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.disciplineChemistry
thesis.degree.grantorColorado State University
thesis.degree.levelDoctoral
thesis.degree.nameDoctor of Philosophy (Ph.D.)

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