The total synthesis of (+/-)-aspirochlorine
| dc.contributor.author | Miknis, Gregory Francis, author | |
| dc.contributor.author | Williams, Robert M., advisor | |
| dc.date.accessioned | 2022-11-28T17:44:54Z | |
| dc.date.available | 2022-11-28T17:44:54Z | |
| dc.date.issued | 1993 | |
| dc.description.abstract | Aspirochlorine is a unique epidithiodioxopiperazine isolated from Aspergillus oryzae, Asp. tamarii and Asp. flavus. The molecule contains a highly unusual bicyclo [3.2.2]disulfide ring system which has previously never been prepared. The first total synthesis of (±)-Aspirochlorine was achieved from commercially available 5-chlororesorcinol 324 in 16 steps. The key step in the synthesis was an efficient intramolecular cycloaddition reaction of hydroxamic ester 344 to form the parent spiro [benzofuran-2(3H),2'-piperazine] ring system 345 as a single stereoisomer. In addition the synthesis employed a 2-nitrobenzyl moiety as a novel amide protecting group. The 2-nitrobenzyl group could be removed in 72% yield under photolytic conditions. Synthetic aspirochlorine was identical to natural material in comparison by 1H NMR, IR and HPLC. Comparison of the biological activity of aspirochlorine versus other epidithiodioxopiperazines was investigated as a function of superoxide production. Although aspirochlorine was shown to be capable of producing superoxide as evidenced in DNA plasmid nicking and NBT reduction assays, the observed activity was less than the 6-membered epidithiodioxopiperazines. | |
| dc.format.medium | doctoral dissertations | |
| dc.identifier.uri | https://hdl.handle.net/10217/235844 | |
| dc.language | English | |
| dc.language.iso | eng | |
| dc.publisher | Colorado State University. Libraries | |
| dc.relation | Catalog record number (MMS ID): 991023335309703361 | |
| dc.relation | QK625.M7M44 1993 | |
| dc.relation.ispartof | 1980-1999 | |
| 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.lcsh | Fungal metabolites | |
| dc.subject.lcsh | Aspergillus | |
| dc.title | The total synthesis of (+/-)-aspirochlorine | |
| 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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