A biomimetic synthesis of the lycorine-type Amaryllidaceae alkaloidslycorine (1), caranine (2) and pluviine (3) was attempted. Efforts to obtain a / high yield synthesis of hydroxyenone 4 from phenol 5 or 6 using external nucleophiles to trap the phenoxonium ion 7 or 8 were unsuccessful. / When amide 8 was oxidized with thallium (III) trifluoroacetate (TTFA)in trifluoroacetic acid (TFA), the amide oxygen efficiently trapped thephenoxonium ion 9 to yield oxazine 10 in good yield. All attempts to / convert 10 into 11 failed. Amide 12 was oxidized with TTFA in TFA,a mixture of dienone 13 and enone 14; however, when amide 12 wasoxidized with VOCl(,3) in anhydrous CH(,2)Cl(,2), only dienone 13 was obtained. The oxidation of amide 15 yielded only enoneester 16. The mechanism by / which 13, 14 and 16 were formed and the rationalization of the results were discussed. Attempted cyclization of enoneester 17, ketoester 18, hydroxyenone 19, hydroxyketones 20 and 21 to tetracyclic ketones 22-26, respectively, with lithium piperidide in ThF or by irradiation in DMSO/DMSO('-) were all unsuccessful. / Source: Dissertation Abstracts International, Volume: 42-01, Section: B, page: 0214. / Thesis (Ph.D.)--The Florida State University, 1981.
| Identifer | oai:union.ndltd.org:fsu.edu/oai:fsu.digital.flvc.org:fsu_74392 |
| Contributors | HUDEC, THOMAS TOD., Florida State University |
| Source Sets | Florida State University |
| Detected Language | English |
| Type | Text |
| Format | 121 p. |
| Rights | On campus use only. |
| Relation | Dissertation Abstracts International |
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