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Approches vers la synthèse d'alcaloïdes : par insertion C-H et par une nouvelle réaction de fragmentation de cycloadduits de nitroso Diels-Alder

Abstract : Alkaloids are among the most interesting natural compounds because of their biological and medicinal properties. Among them amaryllidaceae alkaloids and especially clivonine and its analogues bear many under-studied properties and the synthesis of members of this family should allow more advances in this field. Our team is particularly interested in this target since its synthesis could be achieved starting from an enantioselective nitroso Diels-Alder reaction which is a major research topic of our group. Later in the synthesis a second key step would involve an intramolecular C-H insertion. The nitroso Diels-Alder reaction was performed with an enantiomeric excess of 96% and the synthesis was continued to access the key diazo intermediate, starting material for the C-H insertion step. This last reaction did not allow to access the desired products using commercially available catalysts and a collaboration was started with Pr Huw Davies in order to use more advanced catalysts. The final results of this collaboration are not available yet. Meanwhile three other synthetic routes for clivonine were designed and investigated as variants of the original strategy but none of them allowed access to clivonine. However one of those syntheses led to the discovery of a new reactivity of nitroso Diels-Alder cycloadducts: when exposed to organolithium reagents, a β-fragmentation occurs followed by an addition leading to highly fonctionnalized monocyclic products with high diastereoselectivity. This reaction and its scope need to be investigated further but may have applications in total synthesis.
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Submitted on : Friday, December 15, 2017 - 4:55:35 PM
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Rémy Campagne. Approches vers la synthèse d'alcaloïdes : par insertion C-H et par une nouvelle réaction de fragmentation de cycloadduits de nitroso Diels-Alder. Chimie organique. Université Paris Saclay (COmUE), 2017. Français. ⟨NNT : 2017SACLS448⟩. ⟨tel-01665323⟩

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