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

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Hoffmeister,  Laura
Research Department Fürstner, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Fukuda,  Tsutomu
Research Department Fürstner, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Pototschnig,  Gerit
Research Department Fürstner, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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

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Citation

Hoffmeister, L., Fukuda, T., Pototschnig, G., & Fürstner, A. (2015). Total Synthesis of an Exceptional Brominated 4-Pyrone Derivative of Algal Origin: An Exercise in Gold Catalysis and Alkyne Metathesis. Chemistry – A European Journal, 21(12), 4529-4533. doi:10.1002/chem.201500437.


Cite as: http://hdl.handle.net/11858/00-001M-0000-0025-AE76-1
Abstract
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.