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Synthesis of polyprenylated acylphloroglucinols using bridgehead lithiation: the total synthesis of racemic clusianone and a formal synthesis of racemic garsubellin A

Ahmad, Nadia M., Rodeschini, Vincent, Simpkins, Nigel S., Ward, Simon and Blake, Alexander J. 2007. Synthesis of polyprenylated acylphloroglucinols using bridgehead lithiation: the total synthesis of racemic clusianone and a formal synthesis of racemic garsubellin A. The Journal of Organic Chemistry 72 (13) , pp. 4803-4815. 10.1021/jo070388h

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Abstract

The synthesis of polyprenylated phloroglucinol natural products, including clusianone, nemorosone, and garsubellin A, was pursued by a strategy involving construction of a core bicyclo[3.3.1]nonanetrione structure and subsequent elaboration via organolithium intermediates. Appropriate bridged core structures were obtained through the cyclization of a suitably substituted cyclohexanone enol ether or enol silane with malonyl dichloride. Additional substituents were then introduced by means of regioselective lithiation reactions, including the generation of bridgehead enolates, thus enabling the total synthesis of clusianone and also of an advanced intermediate toward nemorosone. In the case of garsubellin A, an additional THF-like ring was elaborated by a biomimetic 5-exo-tet cyclization of an enol ether (or enol) with a side-chain epoxide. This enabled a formal synthesis of racemic garsubellin A by accessing one of the late intermediates in the Danishefsky synthesis.

Item Type: Article
Date Type: Published Online
Status: Published
Schools: Medicine
Publisher: American Chemical Society
ISSN: 0022-3263
Last Modified: 23 Feb 2018 13:36
URI: http://orca-mwe.cf.ac.uk/id/eprint/109404

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