Total synthesis of floresolide B and Δ6,7-Z-floresolide B

Nicolaou, K. C.; Xu, Hao

doi:10.1039/b517385j

Cited by 50 publications

(21 citation statements)

References 15 publications

(7 reference statements)

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“…zum elfgliedrigen Ring von Buddledon A und durch Nicolaou et al. bei der Totalsynthese der Floresolide, wo auch konkurrierende Kreuzmetathese auftrat . Der Einfluss des Abstandes von Hydroxygruppen und Alkenen auf den Verlauf der Ringschlussmetathese wurde für größere Abstände nur exemplarisch untersucht .…”

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Enantioselektive Totalsynthese der Terreumole A und C aus dem Pilz Tricholoma terreum

2016

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Erstmals gelang die enantioselektive Totalsynthese der cytotoxischenM eroterpenoide Terreumol Au nd Ca us dem Gemeinen Erd-Ritterling Tricholoma terreum. Schlüsselschritt ist der Aufbau des zehngliedrigen Rings durchO lefinmetathese zur trisubstituierten Z-Doppelbindung des [8.4.0]-Bicyclus,d ie nur in Abwesenheit freier Hydroxygruppen gelang.( À)-Terreumol Cw urde vollständig diastereoselektiv in das Bisepoxid( À)-Terreumol Aü berführt, das somit ausgehend von 2-Brom-3,4-dimethoxybenzaldehyd in 14 Stufen und einer Gesamtausbeute von 23 %erhalten wurde. Eine Rçntgenstrukturanalyse des p-Benzochinon-Analogons von (À)-Terreumol Abestätigt die absolute Konfiguration der Naturstoffe.Schema 4. Ringschlussmetathesezu(À)-Terreumol C(2). IBX = o-Iodoxybenzoesäure.Schema 5. Oxidation von (À)-Terreumol C(2)zu(À)-Terreumol A(1) und zum p-Benzochinon 25 mit Molekülstruktur im Kristall. mCPBA = meta-Chlorperbenzoesäure.

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Section: Figureunclassified

Enantioselektive Totalsynthese der Terreumole A und C aus dem Pilz Tricholoma terreum

2016

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“…The synthesis of floresolide B ( 40 ) hydroquinone lactone core was performed by employing ring-closing metathesis approach by Briggs and Dudley [50]. The total synthesis of racemic floresolide B was reported by Nicolaou and Xu, who used an olefin metathesis-based strategy for the formation of the macrocyclic lactone portion [51,52]. …”

Section: Introductionmentioning

confidence: 99%

Quinone and Hydroquinone Metabolites from the Ascidians of the Genus Aplidium

et al. 2014

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Ascidians of the genus Aplidium are recognized as an important source of chemical diversity and bioactive natural products. Among the compounds produced by this genus are non-nitrogenous metabolites, mainly prenylated quinones and hydroquinones. This review discusses the isolation, structural elucidation, and biological activities of quinones, hydroquinones, rossinones, longithorones, longithorols, floresolides, scabellones, conicaquinones, aplidinones, thiaplidiaquinones, and conithiaquinones. A compilation of the 13C-NMR spectral data of these compounds is also presented.

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“…Floresolide B (160), a recently discovered natural product isolated from an ascidian of genus Aplidium that exhibits cytotoxicity against KB tumor cells, contains an aromatic ring connected to a [10]-metacyclophane and a seven-membered ring lactone. The lactone bridge present in substrate 158 was installed prior to the metathesis, as substrates without any constraint gave either dimeric products or low yields (Scheme 5.37) [69].…”

Section: Diterpenoidsmentioning

confidence: 99%

Synthesis of Natural Products Containing Macrocycles by Alkene Ring‐Closing Metathesis

Gradillas¹,

Pérez‐Castells²

2010

Metathesis in Natural Product Synthesis

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IntroductionThe impact of metathesis in modern synthetic chemistry is evidenced by the number of publications and reviews that have appeared in the last decade, some of them covering the specific field of macrocyclization in natural product synthesis [1]. It is therefore difficult not to repeat the reports done by other authors or duplicate their critical views on the chemistry. This chapter is exclusively devoted to the total syntheses of natural bioactive macrocycles involving diene and the diene-ene metathesis, and focuses on the reaction conditions used in the macrocyclization key step and on the stereochemical outcome of the reaction. As we shall see, the choice of the catalyst, solvent, temperature, concentration, and reaction time is crucial in these transformations. In addition, we show how subtle variations on the structure of the substrate lead to modifications in the conformational organization of the molecule, which are critical for the success of ring-closing metathesis (RCM). In particular, the substitution pattern, the steric hindrance of the substituents, the ring size to be formed, and the presence of coordinating heteroatoms are particularly important as they have an important influence on the outcome of the reaction. This chapter has been organized around the various families of natural products in order to compare the reaction conditions for compounds bearing structural similarities. We have deliberately decided to reveal only the information regarding the metathesis step and thus not disclose other details of the syntheses.Synthetic efforts toward macrocycles are often laborious and unpractical. The classical strategies involved are macrolactonizations, macrolactamizations, and macroaldolizations. The macrocyclization approach encounters several problems including the competition between the desired intramolecular reaction and intermolecular processes, which result in the formation of polymers. RCM has the advantage of being compatible with a wide variety of functional groups and forming double bonds that can eventually be converted into other functionalities. The main disadvantages are the control of the stereochemistry of the newly formed double bond and the optimization of the yield. On the other hand, the concomitant loss of ethylene makes this reaction highly atom economical and entropically Metathesis in Natural Product Synthesis: Strategies, Substrates and Catalysts. Edited by

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Total synthesis of floresolide B and Δ6,7-Z-floresolide B

Abstract: The total syntheses of the cytotoxin marine natural product floresolide B (1) and its Delta(6,7)-Z isomer (2) have been achieved through an olefin metathesis-based strategy.

Cited by 50 publications

References 15 publications

Enantioselektive Totalsynthese der Terreumole A und C aus dem Pilz Tricholoma terreum

Enantioselektive Totalsynthese der Terreumole A und C aus dem Pilz Tricholoma terreum

Quinone and Hydroquinone Metabolites from the Ascidians of the Genus Aplidium

Synthesis of Natural Products Containing Macrocycles by Alkene Ring‐Closing Metathesis

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