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.

Di Carmine, G., Ragno, D., Brandolese, A., Bortolini, O., Pecorari, D., Sabuzi, F., et al. (2019). Enantioselective desymmetrization of 1,4-dihydropyridines by oxidative NHC catalysis. CHEMISTRY-A EUROPEAN JOURNAL, 25(31), 7469-7474 [10.1002/chem.201901243].

Enantioselective desymmetrization of 1,4-dihydropyridines by oxidative NHC catalysis

Sabuzi, Federica;
2019-06-04

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.
4-giu-2019
Pubblicato
Rilevanza internazionale
Articolo
Esperti anonimi
Settore CHIM/06 - CHIMICA ORGANICA
English
carbenes
density functional calculations
desymmetrization
dihydropyridines
organocatalysis
Di Carmine, G., Ragno, D., Brandolese, A., Bortolini, O., Pecorari, D., Sabuzi, F., et al. (2019). Enantioselective desymmetrization of 1,4-dihydropyridines by oxidative NHC catalysis. CHEMISTRY-A EUROPEAN JOURNAL, 25(31), 7469-7474 [10.1002/chem.201901243].
Di Carmine, G; Ragno, D; Brandolese, A; Bortolini, O; Pecorari, D; Sabuzi, F; Mazzanti, A; Massi, A
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2108/311570
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