Total Synthesis of the Tetracyclic Pyridinium Alkaloid epi ‐Tetradehydrohalicyclamine B
Abstract: The first total synthesis of a tetracyclic marine pyridinium alkaloid hinged on recent advances in chemoselectivity management: While many classical methods failed to afford the perceptively simple pyridine‐containing core of the target, nickel/iridium photoredox dual catalysis allowed the critical C−C bond to be formed in good yield. Likewise, ring closing alkyne metathesis (RCAM) worked well in the presence of the unhindered pyridine despite the innately Lewis acidic Mo (+6) center of the alkylidyne catalyst. Finally, an iridium catalyzed hydrosilylation was uniquely effective in reducing a tertiary amide without compromising an adjacent pyridine and the lateral double bonds; this transformation is largely without precedent. The second strained macrocycle enveloping the core was closed by intramolecular N‐alkylation with formation of the pyridinium unit; the reaction proceeded site‐ and chemoselectively in the presence of an a priori more basic tertiary amine.
- Location
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Deutsche Nationalbibliothek Frankfurt am Main
- Extent
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Online-Ressource
- Language
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Englisch
- Bibliographic citation
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Total Synthesis of the Tetracyclic Pyridinium Alkaloid epi ‐Tetradehydrohalicyclamine B ; day:02 ; month:09 ; year:2022 ; extent:1
Angewandte Chemie / International edition. International edition ; (02.09.2022) (gesamt 1)
- Creator
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Dalling, Andrew G.
Späth, Georg
Fürstner, Alois
- DOI
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10.1002/anie.202209651
- URN
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urn:nbn:de:101:1-2022090215282432317399
- Rights
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Open Access; Der Zugriff auf das Objekt ist unbeschränkt möglich.
- Last update
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15.08.2025, 7:29 AM CEST
Data provider
Deutsche Nationalbibliothek. If you have any questions about the object, please contact the data provider.
Associated
- Dalling, Andrew G.
- Späth, Georg
- Fürstner, Alois
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