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Domino reactions. Asymmetric palladium(II)-catalyzed cyclizations-carbonylations in the synthesis of natural compounds

Abstract : Intramolecular Wacker-type cyclization of unsaturated polyols and aminopolyols represents a powerful method in the synthesis of oxygen- or nitrogen-containing heterocycles.The thesis offers an insight into the systematic study of domino intramolecular palladium(II)-catalyzed cyclization and coupling reaction allowing the implementation of side chains into heterocyclic skeletons along with the formation of two stereocenters in a single step. Different types of coupling partners and reaction conditions were examined, the influence of substrate substituents on diastereoselectivity is discussed. The applications in the synthesis of naturally occuring compounds or their analogs are outlined (anisomycin, varitriol).Palladium(II)-catalyzed oxycarbonylation represents an interesting transformation of unsaturated polyols into bicyclic lactones with tetrahydrofuran structural motif with excellent cis-stereoselectivity.The first example of the use of ionic liquids as reaction media in the asymmetric Pd(II)-catalyzed oxycarbonylation is described. Based on a ligand screening, the chiral bis(oxazoline)-type ligands were successfully used in the Pd(II)-promoted bicyclisationof racemic pent-4-ene-1,3-diol (±)-69a. The kinetic resolution of (±)-69a in the presenceof chiral catalyst and p-benzoquinone under carbon monoxide atmosphere using acetic acid and/or ionic liquid as solvent afforded enantioenriched 2,6-dioxabicyclo[3.3.0]octane-3-ones(R,R)-70a (57% ee) and (S,S)-70a (80% ee), respectively.
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Submitted on : Friday, June 1, 2012 - 10:52:22 AM
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  • HAL Id : tel-00703209, version 1



Jana Dohanosova. Domino reactions. Asymmetric palladium(II)-catalyzed cyclizations-carbonylations in the synthesis of natural compounds. Other. Université Paris Sud - Paris XI; Slovenská technická univerzita (Bratislave), 2012. English. ⟨NNT : 2012PA112082⟩. ⟨tel-00703209⟩



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