First total synthesis of ampullosine, a unique isoquinoline alkaloid isolated from Sepedonium ampullosporum, and of the related permethylampullosine
A straightforward and convenient approach toward the first total synthesis of ampullosine, a structurally unique 3-methylisoquinoline alkaloid isolated from Sepedonium ampullosporum, is reported. Access to the related O-methyl ampullosine methyl ester from a common intermediate is also disclosed....
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| Autores principales: | , , |
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| Formato: | article artículo publishedVersion |
| Lenguaje: | Inglés |
| Publicado: |
Royal Society of Chemistry
2020
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| Materias: | |
| Acceso en línea: | http://hdl.handle.net/2133/19543 http://hdl.handle.net/2133/19543 |
| Aporte de: |
| id |
I15-R121-2133-19543 |
|---|---|
| record_format |
dspace |
| institution |
Universidad Nacional de Rosario |
| institution_str |
I-15 |
| repository_str |
R-121 |
| collection |
Repositorio Hipermedial de la Universidad Nacional de Rosario (UNR) |
| language |
Inglés |
| orig_language_str_mv |
eng |
| topic |
Ampullosine 3-Methyl-isoquinoline-6-carboxylic Acid Isoquinoline Alkaloid Sepedonium ampullosporum Permethylampullosine Biopharmaceutics |
| spellingShingle |
Ampullosine 3-Methyl-isoquinoline-6-carboxylic Acid Isoquinoline Alkaloid Sepedonium ampullosporum Permethylampullosine Biopharmaceutics Vargas, Didier F. Larghi, Enrique Leandro Kaufman, Teodoro Saúl First total synthesis of ampullosine, a unique isoquinoline alkaloid isolated from Sepedonium ampullosporum, and of the related permethylampullosine |
| topic_facet |
Ampullosine 3-Methyl-isoquinoline-6-carboxylic Acid Isoquinoline Alkaloid Sepedonium ampullosporum Permethylampullosine Biopharmaceutics |
| description |
A straightforward and convenient approach toward the first total synthesis of ampullosine, a structurally
unique 3-methylisoquinoline alkaloid isolated from Sepedonium ampullosporum, is reported. Access to
the related O-methyl ampullosine methyl ester from a common intermediate is also disclosed. The
synthetic sequence toward the natural product comprised a Kolbe-type carboxylation of 3,5-
dihydroxybenzoic acid and further esterification of the diacid, followed by masking of one of the phenols
through selective ester reduction and subsequent acetonide formation. Installation of the three-carbon
atom required for the 3-methylpyridine ring was performed by triflation of the remaining free phenol
and a Pd-catalyzed Suzuki–Miyaura reaction with potassium E-propenyltrifluoroborate. Deprotection of
the acetonide, followed by partial oxidation of the benzylic alcohol to the salicylaldehyde, O-methylation
of the free phenol and hydrazonation of the resulting ortho-anisaldehyde derivative gave a hydrazonebased 1-azatriene. This was further subjected to 6p-azaelectrocyclization to afford
permethylampullosine (11 steps, 14% overall yield), whereas exhaustive demethylation with AlI3 generated
in situ gave ampullosine (12 steps, 3.2% global yield). |
| format |
article artículo publishedVersion |
| author |
Vargas, Didier F. Larghi, Enrique Leandro Kaufman, Teodoro Saúl |
| author_facet |
Vargas, Didier F. Larghi, Enrique Leandro Kaufman, Teodoro Saúl |
| author_sort |
Vargas, Didier F. |
| title |
First total synthesis of ampullosine, a unique isoquinoline alkaloid isolated from Sepedonium ampullosporum, and of the related permethylampullosine |
| title_short |
First total synthesis of ampullosine, a unique isoquinoline alkaloid isolated from Sepedonium ampullosporum, and of the related permethylampullosine |
| title_full |
First total synthesis of ampullosine, a unique isoquinoline alkaloid isolated from Sepedonium ampullosporum, and of the related permethylampullosine |
| title_fullStr |
First total synthesis of ampullosine, a unique isoquinoline alkaloid isolated from Sepedonium ampullosporum, and of the related permethylampullosine |
| title_full_unstemmed |
First total synthesis of ampullosine, a unique isoquinoline alkaloid isolated from Sepedonium ampullosporum, and of the related permethylampullosine |
| title_sort |
first total synthesis of ampullosine, a unique isoquinoline alkaloid isolated from sepedonium ampullosporum, and of the related permethylampullosine |
| publisher |
Royal Society of Chemistry |
| publishDate |
2020 |
| url |
http://hdl.handle.net/2133/19543 http://hdl.handle.net/2133/19543 |
| work_keys_str_mv |
AT vargasdidierf firsttotalsynthesisofampullosineauniqueisoquinolinealkaloidisolatedfromsepedoniumampullosporumandoftherelatedpermethylampullosine AT larghienriqueleandro firsttotalsynthesisofampullosineauniqueisoquinolinealkaloidisolatedfromsepedoniumampullosporumandoftherelatedpermethylampullosine AT kaufmanteodorosaul firsttotalsynthesisofampullosineauniqueisoquinolinealkaloidisolatedfromsepedoniumampullosporumandoftherelatedpermethylampullosine |
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Repositorios |
| _version_ |
1764820410936852482 |