PALLADIUM : REACTIVITE DE CARBONATES DE DIENOLS ALLYLIQUES APPROCHE SYNTHETIQUE DE LA (−)-PATEAMINE A

Abstract : Since its introduction by Tsuji et al. in the 60s, the palladium catalyzed allylic alkylation has become a powerful tool for the construction of C-C bonds. For our part, we applied this reaction to new types of substrates, namely allyl dienol carbonates. Optimization of the reaction conditions allowed a straightforward access to α,α-disubstituted butenolides in a highly regio- and enantioselective fashion. These butenolides were then subjected to a [3,3] sigmatropic Cope rearrangement or to a reduction/oxidation sequence to afford the corresponding γ-substituted furanones or β-disubstituted γ-butyrolactones, respectively. In order to demonstrate the synthetic utility of this method, the reaction was eventually applied to the total synthesis of (−)-nephrosteranic acid and (−)-roccelaric acid. Finally, the palladium-catalyzed allylic alkylation was incorporated in a one-pot four steps sequence, including a Cope rearrangement and a nucleophilic addition to effectively afford polysubstituted furans and pyrroles. A synthetic approach of (−)-pateamine A and its analog, des-methyl-des-amino patéamine A (DMDA-pateamine A) was also studied. We managed to synthesize and couple the three fragments that constitute the macrocycle of DMDA pateamine A. The key step of the synthesis, consisting in a diene-ene ring closing metathesis, was also tested yielding the desired macrocycle. Finally, an advanced intermediate of the side chain was synthesized starting from geraniol.
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Submitted on : Monday, November 18, 2013 - 7:10:15 PM
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Jérémy Fournier. PALLADIUM : REACTIVITE DE CARBONATES DE DIENOLS ALLYLIQUES APPROCHE SYNTHETIQUE DE LA (−)-PATEAMINE A. Chimie organique. Université Pierre et Marie Curie - Paris VI, 2013. Français. ⟨pastel-00905915⟩

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