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Total Synthesis of (−)-Salicylihalamide

MPG-Autoren
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Fürstner,  Alois
Research Department Fürstner, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Dierkes,  Thorsten
Research Department Fürstner, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Thiel,  Oliver R.
Research Department Fürstner, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

Blanda,  Gaetano
Research Department Fürstner, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Zitation

Fürstner, A., Dierkes, T., Thiel, O. R., & Blanda, G. (2001). Total Synthesis of (−)-Salicylihalamide. Chemistry – A European Journal, 7(24), 5286-5298. doi:10.1002/1521-3765(20011217)7:24<5286:AID-CHEM5286>3.0.CO;2-G.


Zitierlink: http://hdl.handle.net/11858/00-001M-0000-0024-4528-5
Zusammenfassung
A concise total synthesis of the potent cytotoxic marine natural products salicylihalamide A and B (1 a, b) is reported. Key steps of our approach were the asymmetric hydrogenation reactions of β-keto esters 18 and 32 catalyzed by [((S)-BINAP)RuCl2]2⋅NEt3 and the cyclization of the macrolide core by ring closing olefin metathesis (RCM) using the “second-generation” ruthenium carbene complex 24 as the catalyst which bears an imidazol-2-ylidene ligand. The E/Z ratio obtained in this macrocyclization reaction was determined by the protecting groups at the remote phenolic OH group of the cyclization precursor. The elaboration of the resulting cycloalkene 37 into the final target involved a CrCl2-mediated synthesis of vinyliodide 49 which, after deprotection, did undergo a copper-catalyzed cross-coupling process with the (Z,Z)-configurated carboxamide 42 to form the labile enamide moiety of 1. Compound 42 was derived from a palladium-catalyzed Negishi coupling between butynylzinc chloride and 3-iodoacrylate 39 followed by a Lindlar reduction of enyne 40 thus obtained and a final aminolysis of the ester group.