Origin of the Enantioselectivity in Organocatalytic Michael Additions of beta-Ketoamides to alpha,beta-Unsaturated Carbonyls: A Combined Experimental, Spectroscopic and Theoretical Study - Aix-Marseille Université Accéder directement au contenu
Article Dans Une Revue Chemistry - A European Journal Année : 2015

Origin of the Enantioselectivity in Organocatalytic Michael Additions of beta-Ketoamides to alpha,beta-Unsaturated Carbonyls: A Combined Experimental, Spectroscopic and Theoretical Study

Résumé

The organocatalytic enantioselective conjugate addition of secondary β-ketoamides to α,β-unsaturated carbonyl compounds is reported. Use of bifunctional Takemoto’s thiourea catalyst allows enantiocontrol of the reaction leading either to simple Michael adducts or spirocyclic aminals in up to 99 % ee. The origin of the enantioselectivity has been rationalised based on combined DFT calculations and kinetic analysis. This study provides a deeper understanding of the reaction mechanism, which involves a predominant role of the secondary amide proton, and clarifies the complex interactions occurring between substrates and the catalyst.

Dates et versions

hal-01133609 , version 1 (19-03-2015)

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Citer

Adrien Quintard, Diana Cheshmedzhieva, Maria del Mar Sanchez Duque, Anouk Gaudel-Siri, Jean-Valère Naubron, et al.. Origin of the Enantioselectivity in Organocatalytic Michael Additions of beta-Ketoamides to alpha,beta-Unsaturated Carbonyls: A Combined Experimental, Spectroscopic and Theoretical Study. Chemistry - A European Journal, 2015, 21, pp.778-790. ⟨10.1002/chem.201404481⟩. ⟨hal-01133609⟩
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