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Journal Articles Journal of Natural Products Year : 2013

Regio- and stereocontrolled synthesis of oligostilbenoids: theoretical highlights at the supramolecular level.

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Abstract

Oligostilbenoids (e.g., ampelopsin F, viniferin, pallidol) result from homogeneous or heterogeneous coupling of monomeric stilbenoid units, leading to various chemical structures. Oligostilbenoid synthesis is regio- and stereocontrolled. To tackle this regio- and stereocontrol, a supramolecular chemistry approach is required that can be achieved by quantum chemistry. The stability of noncovalent π-stacks, formed between two stilbenoid units prior to oxidation, is accurately evaluated with density functional theory (DFT) including dispersive effects (within the DFT-D formalism). These noncovalent arrangements drive the regiocontrol. The rest of the chemical pathway is a succession of dearomatization and rearomatization stages. The thermodynamics and kinetics of the processes are calculated with classical hybrid functionals. This study allows discrimination between the two main possible chemical pathways, namely, radical-neutral and radical-radical reactions. The former appears more likely, thermodynamics and kinetics being in perfect agreement with the experimental 1:2 ratio obtained for ampelopsin F:pallidol analogues, respectively.
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Dates and versions

inserm-00926247 , version 1 (09-01-2014)

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Saraswati S. Velu, Florent Di Meo, Patrick Trouillas, Juan-Carlos Sancho-Garcia, Jean-Frédéric F. Weber. Regio- and stereocontrolled synthesis of oligostilbenoids: theoretical highlights at the supramolecular level.. Journal of Natural Products, 2013, 76 (4), pp.538-46. ⟨10.1021/np300705p⟩. ⟨inserm-00926247⟩
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