Total Synthesis of Neurymenolide A Based on a Gold‐Catalyzed Synthesis of 4‐Hydroxy‐2‐pyrones

Chaładaj, Wojciech; Corbet, Matthieu; Fürstner, Alois

doi:10.1002/anie.201203180

Cited by 144 publications

(71 citation statements)

References 64 publications

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“…Both enantiomers of these compounds are accessible from the corresponding enantiomers of the aldehydes used in our modular strategy. A very efficient Gold-catalyzed intramolecular cyclization to the 4-hydroxy-2-pyrone motif that was applied in the total synthesis of the complex natural product neurymenolide A was recently reported by Fürstner and co-workers, [40] and the use of Gold catalysis for the synthesis of pyrones has also recently been reviewed. The limitation of the method is demonstrated in the case of phomapyrone B that was thus synthesized via an alternative route with high enantiomeric purity, which allowed to determine the absolute configuration of the natural product as (R)-(-)-phomapyrone B.…”

Section: Discussionmentioning

confidence: 99%

Synthesis and Absolute Configuration of Natural 2‐Pyrones

Burkhardt

Dickschat

2018

Eur J Org Chem

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2‐Pyrones are frequently produced by microorganisms and often exhibit interesting bioactivities. Therefore, a short and easy synthetic access to these natural products is desirable. Synthetic routes to nectriapyrone, gibepyrone A, racemic gulypyrone A, (+)‐germicidin C, (ent)‐desoxygermicidin C and (ent)‐prolipyrone A via a modular approach are presented, allowing the assignment of the absolute configurations of the latter three chiral compounds. The method failed for the synthesis of (ent)‐phomapyrone B that was thus synthesized via a different route, resulting in an assignment of the absolute configuration of natural phomapyrone B.

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Section: Discussionmentioning

confidence: 99%

Synthesis and Absolute Configuration of Natural 2‐Pyrones

Burkhardt

Dickschat

2018

Eur J Org Chem

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“…For this very reason it was planned to forge this characteristic heterocyclic ring system by re‐programming a gold catalyzed procedure previously developed by our group for the preparation of 2‐pyrones G (Scheme , bottom) 12–14. This transformation hinges on a 6‐ endo‐dig cyclization of alkynoic β‐ketoesters (R 2 = t Bu).…”

Section: Methodsmentioning

confidence: 99%

Total Synthesis of an Exceptional Brominated 4‐Pyrone Derivative of Algal Origin: An Exercise in Gold Catalysis and Alkyne Metathesis

Hoffmeister

Fukuda

Pototschnig

et al. 2015

Chemistry A European J

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A concise approach to the algal metabolite 1 is described, which also determines the previously unknown stereostructure of this natural product. Compound 1 is distinguished by a rare brominated 4-pyrone nucleus linked as a ketene–acetal to a polyunsaturated macrocyclic scaffold comprising an extra homoallylic bromide entity. The synthesis of 1 is based on the elaboration and selective functionalization of the linear precursor 23 endowed with no less than six different sites of unsaturation including the highly enolized oxo-alkanoate function. Key to success was the formation of the 2-alkoxy-4-pyrone ring by a novel gold-catalyzed transformation which engages only the acetylenic β-ketoester substructure of 23 but leaves all other π-bonds untouched. The synthesis was completed by a ring-closing alkyne metathesis to forge the signature cycloalkyne motif of 1 followed by selective bromination of the ketene–acetal site in the resulting product 27 without touching the skipped diene–yne substructure resident within the macrocyclic tether

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“…It might also be possible that the POM is basic enough to also capture the proton of the oxonium vinylgold intermediate B (Scheme b). The proto‐deauration of the vinylgold bond in B would thus become a slow rate‐limiting step because it requires the deprotonation of the POM surface of C 15. This would also explain why stronger bases reduce the reactivity even more.…”

Section: Methodsmentioning

confidence: 99%