Investigations of an annulation-fragmentation-spirocyclisation approach to fawcettimine-type Lycopodium alkaloids
This paper reports progress in the development of a furan oxidative N-spirocyclisation approach to the fawcettimine alkaloids huperzine Q and lycopladine D. A short synthesis is described of a key intermediate cyclopentaindolizidine that subsequently fragments by N-acylation and β-elimination. The s...
| Hlavní autoři: | , |
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| Médium: | Journal article |
| Jazyk: | English |
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Elsevier
2019
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| _version_ | 1826285182043291648 |
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| author | Seah, KY Robertson, J |
| author_facet | Seah, KY Robertson, J |
| author_sort | Seah, KY |
| collection | OXFORD |
| description | This paper reports progress in the development of a furan oxidative N-spirocyclisation approach to the fawcettimine alkaloids huperzine Q and lycopladine D. A short synthesis is described of a key intermediate cyclopentaindolizidine that subsequently fragments by N-acylation and β-elimination. The stereochemistry of 1,4-addition of cyanide to the resulting enone is discussed with supporting molecular modelling calculations. N-Deprotection is shown to be accompanied by cyclisation onto the nitrile group, resulting in a tricyclic lactam with a twisted amide functionality. Elaboration of this lactam afforded four of the five rings present in lycopladine D with just the C(8) carbon lacking.
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| first_indexed | 2024-03-07T01:25:00Z |
| format | Journal article |
| id | oxford-uuid:91abedbe-ed1b-43a5-85fd-95e40d9c28c0 |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-07T01:25:00Z |
| publishDate | 2019 |
| publisher | Elsevier |
| record_format | dspace |
| spelling | oxford-uuid:91abedbe-ed1b-43a5-85fd-95e40d9c28c02022-03-26T23:20:12ZInvestigations of an annulation-fragmentation-spirocyclisation approach to fawcettimine-type Lycopodium alkaloidsJournal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:91abedbe-ed1b-43a5-85fd-95e40d9c28c0EnglishSymplectic Elements at OxfordElsevier2019Seah, KYRobertson, JThis paper reports progress in the development of a furan oxidative N-spirocyclisation approach to the fawcettimine alkaloids huperzine Q and lycopladine D. A short synthesis is described of a key intermediate cyclopentaindolizidine that subsequently fragments by N-acylation and β-elimination. The stereochemistry of 1,4-addition of cyanide to the resulting enone is discussed with supporting molecular modelling calculations. N-Deprotection is shown to be accompanied by cyclisation onto the nitrile group, resulting in a tricyclic lactam with a twisted amide functionality. Elaboration of this lactam afforded four of the five rings present in lycopladine D with just the C(8) carbon lacking. |
| spellingShingle | Seah, KY Robertson, J Investigations of an annulation-fragmentation-spirocyclisation approach to fawcettimine-type Lycopodium alkaloids |
| title | Investigations of an annulation-fragmentation-spirocyclisation approach to fawcettimine-type Lycopodium alkaloids |
| title_full | Investigations of an annulation-fragmentation-spirocyclisation approach to fawcettimine-type Lycopodium alkaloids |
| title_fullStr | Investigations of an annulation-fragmentation-spirocyclisation approach to fawcettimine-type Lycopodium alkaloids |
| title_full_unstemmed | Investigations of an annulation-fragmentation-spirocyclisation approach to fawcettimine-type Lycopodium alkaloids |
| title_short | Investigations of an annulation-fragmentation-spirocyclisation approach to fawcettimine-type Lycopodium alkaloids |
| title_sort | investigations of an annulation fragmentation spirocyclisation approach to fawcettimine type lycopodium alkaloids |
| work_keys_str_mv | AT seahky investigationsofanannulationfragmentationspirocyclisationapproachtofawcettiminetypelycopodiumalkaloids AT robertsonj investigationsofanannulationfragmentationspirocyclisationapproachtofawcettiminetypelycopodiumalkaloids |