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Décanolides hydroxylés : nouvelles approches synthétiques et glycosylation par de nouveaux réactifs à base d'iode hypervalent

Abstract : During this co-direction Ph.D. thesis we were interested both in:
(i) New synthetic approaches towards hydroxylated 10-membered macrolactones, involving two key-steps: formation of a bicyclic heteroadduct and its oxidative fragmentation.
(ii) Glycosylation of natural 9-decanolides using a methodology based on tagged hypervalent iodine reagents.
The multi-step synthesis part of this work required a study for the inverse electronic demand heterocycloaddition reaction. Therefore, we synthesized new heterodienes, aiming to favour endo configured bicyclic adducts, which showed unique reactivity, and may lead to structural diversity. In this process, we developed a new cyclohexanone-derived chiral dienophile bearing oxazolidinone moiety, which was subjected to Eu(fod)3-catalyzed heterocycloaddition with methyl arylidenepyruvates to afford the desired adduct in good yields. The reaction proceeds with high facial and endo double stereocontrol. These results were then applied to access natural 10-membered macrolactones (such as decarestrictines or herbarumins).
In the second part of this work, we have synthesized novel hypervalent iodine reagents tagged with iso-butyl sulfonate group. This particular group allows the scavenging of the hypervalent iodine species and especially their by-products. Nucleophilic substitution occuring at the sulfonate group by an azide ion exchange resin allows indeed this scavenging. Four sulfonate-tagged iodanes were prepared and applied to several reactions, including oxidative fragmentation of bicycles and O-glycosylation of polyfunctional alcohols. Using this reaction, hybrid molecules bearing both decarestrictine and sugar moiety were quickly obtained with limited purification step based on the scavenging methodology.
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Submitted on : Tuesday, January 8, 2008 - 7:16:44 PM
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  • HAL Id : tel-00203092, version 1

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Florian Gallier. Décanolides hydroxylés : nouvelles approches synthétiques et glycosylation par de nouveaux réactifs à base d'iode hypervalent. Autre. Université du Maine, 2007. Français. ⟨tel-00203092⟩

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