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Development of Heterogeneous Enantioselective Catalysts using Chiral Metal-Organic Frameworks MOFs
Published on: January 17, 2020
Enantioselective Desymmetrization of 1,4-Dihydropyridines by Oxidative NHC Catalysis
Graziano Di Carmine1, Daniele Ragno1, Arianna Brandolese1
1Department of Chemical and Pharmaceutical Sciences, University of Ferrara, Via L. Borsari 46, I-44121, Ferrara, Italy.
Abstract:
The unprecedented desymmetrization of prochiral dialdehydes catalyzed by N-heterocyclic carbenes under oxidative conditions was applied to the highly enantioselective synthesis of 1,4-dihydropyridines (DHPs) starting from 3,5-dicarbaldehyde substrates. Synthetic elaboration of the resulting 5-formyl-1,4-DHP-3-carboxylates allowed for access to the class of pharmaceutically relevant 1,4-DHP-3,5-dicarboxylates (Hantzsch esters). DFT calculations suggested that the enantioselectivity of the process is determined by the transition state involving the oxidation of the Breslow intermediate by the external quinone oxidant.
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