Solvent-Induced Reversal of Enantioselectivity in the Synthesis of Succinimides by the Addition of Aldehydes to Maleimides Catalysed by Carbamate-Monoprotected 1,2-Diamines

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Title: Solvent-Induced Reversal of Enantioselectivity in the Synthesis of Succinimides by the Addition of Aldehydes to Maleimides Catalysed by Carbamate-Monoprotected 1,2-Diamines
Authors: Flores Ferrándiz, Jesús | Fiser, Béla | Gómez Bengoa, Enrique | Chinchilla, Rafael
Research Group/s: Catálisis Estereoselectiva en Síntesis Orgánica (CESO)
Center, Department or Service: Universidad de Alicante. Departamento de Química Orgánica | Universidad de Alicante. Instituto Universitario de Síntesis Orgánica
Keywords: Asymmetric catalysis | Organo­catalysis | Michael addition | Enantioselectivity | Solvent effects | Transition states
Knowledge Area: Química Orgánica
Issue Date: Feb-2015
Publisher: Wiley-VCH Verlag GmbH & Co. KGaA
Citation: European Journal of Organic Chemistry. 2015, 6: 1218-1225. doi:10.1002/ejoc.201403415
Abstract: A simple change in the polarity of the solvent allows both enantiomers of substituted succinimides to be obtained in the enantioselective conjugate addition reaction of aldehydes, mainly α,α-disubstituted, to maleimides catalysed by chiral carbamate-monoprotected trans-cyclohexane-1,2-diamines. Using a single enantiomer of the organocatalyst, both enantiomers of the resulting Michael adducts are obtained in high yields by simply changing the reaction solvent from aqueous DMF (up to 84 % ee) to chloroform (up to 86 % ee). Theoretical calculations are used to explain this uncommon reversal of the enantioselectivity; two transition state orientations of different polarities are differently favoured in polar or nonpolar solvents.
Sponsor: The authors are grateful for the financial support from the Spanish Ministerio de Economía y Competitividad (MEC) (project number CTQ2011-24151), Fondos Europeos para el Desarrollo Regional (FEDER), the COST Action CM0905 “Organocatalysis”, the FP7 Marie Curie Action of the European Commission via the ITN ECHONET Network (FP7-MCITN-2012-316379), the University of Alicante and the University of the Basque Country.
URI: http://hdl.handle.net/10045/52887
ISSN: 1434-193X (Print) | 1099-0690 (Online)
DOI: 10.1002/ejoc.201403415
Language: eng
Type: info:eu-repo/semantics/article
Rights: © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Peer Review: si
Publisher version: http://dx.doi.org/10.1002/ejoc.201403415
Appears in Collections:INV - CESO - Artículos de Revistas
Research funded by the EU

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