Cargando…
Total Synthesis of Alkaloid 205B
[Image: see text] Concise and highly stereocontrolled total syntheses of racemic and enantiopure frog alkaloid 205B (1) were accomplished in 11 steps from 4-methoxypyridines 6 and 7 in overall yields of 8 and 8%, respectively. The assembly of the core of the natural product relies on a stereoselecti...
Autores principales: | , |
---|---|
Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical
Society
2014
|
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4184464/ https://www.ncbi.nlm.nih.gov/pubmed/25180567 http://dx.doi.org/10.1021/jo501415r |
_version_ | 1782337844645199872 |
---|---|
author | Tsukanov, Sergey V. Comins, Daniel L. |
author_facet | Tsukanov, Sergey V. Comins, Daniel L. |
author_sort | Tsukanov, Sergey V. |
collection | PubMed |
description | [Image: see text] Concise and highly stereocontrolled total syntheses of racemic and enantiopure frog alkaloid 205B (1) were accomplished in 11 steps from 4-methoxypyridines 6 and 7 in overall yields of 8 and 8%, respectively. The assembly of the core of the natural product relies on a stereoselective Tsuji–Trost allylic amination reaction and a ring-closing metathesis. The synthesis features the use of an N-acylpyridinium salt reaction to introduce the first stereocenter and an unprecedented trifluoroacetic anhydride-mediated addition of an allylstannane to a vinylogous amide with complete facial selectivity. Deoxygenation of the C4 ketone proved difficult but was accomplished via a modified Barton–McCombie reaction in the presence of a catalytic amount of diphenyl diselenide. |
format | Online Article Text |
id | pubmed-4184464 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2014 |
publisher | American Chemical
Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-41844642015-09-02 Total Synthesis of Alkaloid 205B Tsukanov, Sergey V. Comins, Daniel L. J Org Chem [Image: see text] Concise and highly stereocontrolled total syntheses of racemic and enantiopure frog alkaloid 205B (1) were accomplished in 11 steps from 4-methoxypyridines 6 and 7 in overall yields of 8 and 8%, respectively. The assembly of the core of the natural product relies on a stereoselective Tsuji–Trost allylic amination reaction and a ring-closing metathesis. The synthesis features the use of an N-acylpyridinium salt reaction to introduce the first stereocenter and an unprecedented trifluoroacetic anhydride-mediated addition of an allylstannane to a vinylogous amide with complete facial selectivity. Deoxygenation of the C4 ketone proved difficult but was accomplished via a modified Barton–McCombie reaction in the presence of a catalytic amount of diphenyl diselenide. American Chemical Society 2014-09-02 2014-10-03 /pmc/articles/PMC4184464/ /pubmed/25180567 http://dx.doi.org/10.1021/jo501415r Text en Copyright © 2014 American Chemical Society Terms of Use (http://pubs.acs.org/page/policy/authorchoice_termsofuse.html) |
spellingShingle | Tsukanov, Sergey V. Comins, Daniel L. Total Synthesis of Alkaloid 205B |
title | Total Synthesis of Alkaloid
205B |
title_full | Total Synthesis of Alkaloid
205B |
title_fullStr | Total Synthesis of Alkaloid
205B |
title_full_unstemmed | Total Synthesis of Alkaloid
205B |
title_short | Total Synthesis of Alkaloid
205B |
title_sort | total synthesis of alkaloid
205b |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4184464/ https://www.ncbi.nlm.nih.gov/pubmed/25180567 http://dx.doi.org/10.1021/jo501415r |
work_keys_str_mv | AT tsukanovsergeyv totalsynthesisofalkaloid205b AT cominsdaniell totalsynthesisofalkaloid205b |