Concise Asymmetric Syntheses of Streptazone A and Abikoviromycin**
| Autor: | Nikolaj L. Villadsen, Gustav J. Wørmer, Peter Nørby, Thomas B. Poulsen |
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| Rok vydání: | 2021 |
| Předmět: |
Pyridines
natural products 010402 general chemistry Ring (chemistry) 01 natural sciences Catalysis electrophile chemistry.chemical_compound transition metal catalysis Cyclopentadienone Reactivity (chemistry) total synthesis Molecular Structure 010405 organic chemistry Enantioselective synthesis asymmetric catalysis Total synthesis Stereoisomerism General Medicine General Chemistry Combinatorial chemistry 0104 chemical sciences chemistry Electrophile Abikoviromycin |
| Zdroj: | Wørmer, G J, Villadsen, N L, Nørby, P & Poulsen, T B 2021, ' Concise Asymmetric Syntheses of Streptazone A and Abikoviromycin** ', Angewandte Chemie-International Edition, vol. 60, no. 19, pp. 10521-10525 . https://doi.org/10.1002/anie.202101439 Wørmer, G J, Villadsen, N L, Poulsen, T & Nørby, P 2021, ' Concise asymmetric syntheses of streptazone A and abikoviromycin ', 21st Tetrahedron Symposium, 21/06/2021-24/06/2021 . Aarhus University |
| ISSN: | 1521-3773 1433-7851 |
| Popis: | Streptazone A and abikoviromycin are related alkaloids that both feature an unusual arrangement of reactive functionalities within an underlying compact tricyclic ring system. Here, we report a highly concise asymmetric synthesis of both natural products. The developed route first constructs another member of the streptazones, streptazone B1, using a rhodium-catalyzed distal selective allene-ynamide Pauson-Khand reaction as the key transformation. A regio- and enantioselective epoxidation under chiral phase-transfer catalytic conditions was then achieved to directly make streptazone A in 8 steps overall. A chemoselective, iridium-catalyzed reduction of the enaminone-system was employed to make abikoviromycin in one additional step. Studies of the intrinsic reactivity of streptazone A towards the cysteine mimic, N-acetylcysteamine, revealed unanticipated transformations, resulting in thiol conjugation to both the hindered tertiary carbon of the double allylic epoxide and in bis-thiol conjugation which may proceed via formation of a cyclopentadienone intermediate. With flexible access to these compounds, studies aimed to identify their direct biological targets are now possible. |
| Databáze: | OpenAIRE |
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