Totalsynthese des Antibiotikums Kendomycin durch Photo‐Fries‐Umlagerung und Ringschlussmetathese

Magauer, Thomas; Martin, Harry J.; Mulzer, Johann

doi:10.1002/ange.200900522

Cited by 25 publications

(9 citation statements)

References 36 publications

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“…[186] Mehrfach wurde die Photo-Fries-Umlagerung in der Synthese polycyclischer Hydroxychinone genutzt. Zu diesen zählen (AE )-Griseofulvin, [187] Islandicin, [188] Bikaverin [189] und Spinochrom A.…”

Section: Photo-fries-umlagerungenunclassified

Photochemische Reaktionen als Schlüsselschritte in der Naturstoffsynthese

2011

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Photochemische Reaktionen bereichern in signifikanter Weise das Repertoire zur Knüpfung von Kohlenstoff‐Kohlenstoff‐Bindungen und machen ungewöhnliche, auf herkömmlichem Weg nicht erhältliche Molekülgerüste zugänglich. In diesem Aufsatz werden die wichtigsten Umsetzungen der Photochemie vorgestellt, die auf breiter Front Einzug in die Naturstoffsynthese gehalten haben. Beispielhaft werden einzelne Totalsynthesen diskutiert, wobei besonderes Augenmerk auf den photochemischen Schlüsselschritt sowie dessen Stereoselektivität gerichtet ist. Dabei wird das photochemisch erzeugte Molekül in Relation zur Struktur des Naturstoffs gebracht, und Folgereaktionen werden, wo notwendig, illustriert und klassifiziert.

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Section: Photo-fries-umlagerungenunclassified

Photochemische Reaktionen als Schlüsselschritte in der Naturstoffsynthese

2011

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“…This elimination process was accelerated by the addition of a small amount of water. The compound 23 has the same skeleton as intermediates obtained by the groups of Lee7a and Mulzer 7e,f. Finally, the selective removal of the phenolic TBS group, oxidation, and acidic rearrangement of the resulting o ‐quinone, with the simultaneous TBS removal, accomplished the total synthesis of kendomycin.…”

Section: Methodsmentioning

confidence: 82%

“…The macrocyclic carbon framework of 1 represents a major challenge for an efficient chemical synthesis. Among all the achieved total syntheses and formal total syntheses, several macrocyclization strategies, including C‐glycosydation,7a ring‐closing metathesis (RCM),7b,c,e,f, 8 the Barbier reaction,7d photo‐Fries rearrangement,7e,f Dötz benzannulation,7g and Prins reaction7h have been reported, albeit in modest yields. We have attempted an RCM strategy for the macrocyclization at the C13C14 double bond of 1 8.…”

Section: Methodsmentioning

confidence: 99%

Total Synthesis of the Antibiotic Kendomycin: A Macrocyclization Using the Tsuji–Trost Etherification

Sengoku

Ogura

et al. 2014

Angewandte Chemie

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A highly stereocontrolled, convergent total synthesis of kendomycin [(À)-TAN2162], an ansa-macrocyclic antibiotic, is reported. The key of the strategy is an unprecedented Tsuji-Trost macrocyclic etherification, followed by a transannular Claisen rearrangement to construct the 18-membered carbocyclic framework. The oxa-six-and five-membered rings were also stereoselectively constructed respectively by a cascade oxidative cyclization at an unfunctionalized benzylic position and using a one-pot epoxidation/5-exo-tet epoxide opening. Scheme 1. Retrosynthetic analysis. TBS = tert-butyldimethylsilyl.Scheme 4. Complete total synthesis of 1. mCPBA = m-chloroperoxybenzoic acid, TBAF = tetra-n-butylammonium fluoride. Angewandte Chemie 4299

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“…A gold-catalyzed benzofuran synthesis was applied in the formal total synthesis of Kendomycin (À)-TAN 2162), [38] a carbocyclic ansa-compound isolated from Streptomyces, via the preparation of Mulzer's [39] initially attempted to furnish the 5-endo-dig cyclisation with PtCl 2 which failed to deliver 24. By applying the more electrophilic JohnPhosAuOTs catalyst 24 was obtained in an excellent yield of 79 % completing the formal total synthesis of Kendomycin (Scheme 9b).…”

Section: Hydroalkoxylationmentioning

confidence: 99%