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Approche Générale, Efficace et Sélective de Produits Naturels Possédant le Squelette Bicyclo[5.3.0]décane : Synthèse d'Azulènes et de Guaianolides

Abstract : The [2+2] cycloaddition of dichloroketene and monosubstituted cycloheptatrienes, followed by ring expansion with diazomethane and dehydrohalogenation, affords alpha-chlorotrienones in a regio- and stereoselective manner. These compounds are attractive synthons for the efficient total synthesis of natural products containing the bicyclo[5.3.0]decane skeleton. An efficient and regioselective approach to polysubstituted azulènes, including natural azulenes such as guaiazulene and chamazulene carboxylic acid, from these alpha-chlorotrienones, has been achieved with organozinc reagents, ketene acetals and Suzuki coupling reagents. This methodology, also used for azaazulene synthesis, involved as well a new method of direct aromatization. After optimization of our (+/-)-6-déoxygeigérin synthesis, we achieved the first total synthesis of (+/-)-geigérin in a highly stereoselective manner, thereby opening a flexible route to the natural 6-12 and 8-12 guaianolides. Thus, this approach seems to be particularly effective for the synthesis of numerous natural guaianes, and perhaps even for diterpene synthesis.
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https://tel.archives-ouvertes.fr/tel-00405746
Contributor : Sébastien Carret <>
Submitted on : Tuesday, July 21, 2009 - 10:18:29 AM
Last modification on : Friday, November 6, 2020 - 3:56:30 AM
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Sébastien Carret. Approche Générale, Efficace et Sélective de Produits Naturels Possédant le Squelette Bicyclo[5.3.0]décane : Synthèse d'Azulènes et de Guaianolides. Chimie. Université Joseph-Fourier - Grenoble I, 2005. Français. ⟨tel-00405746⟩

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