Remote Substituent Effects on the Stereoselectivity and Organocatalytic Activity of Densely Substituted Unnatural Proline Esters in Aldol Reactions

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Title: Remote Substituent Effects on the Stereoselectivity and Organocatalytic Activity of Densely Substituted Unnatural Proline Esters in Aldol Reactions
Authors: Retamosa Hernández, María de Gracia | Cózar Ruano, Abel de | Sánchez, Mirian | Miranda, José I. | Sansano, Jose M. | Castelló Moncayo, Luis Miguel | Nájera, Carmen | Jiménez, Ana I. | Sayago, Francisco J. | Cativiela, Carlos | Cossío Mora, Fernando Pedro
Research Group/s: Síntesis Asimétrica (SINTAS)
Center, Department or Service: Universidad de Alicante. Departamento de Química Orgánica | Universidad de Alicante. Instituto Universitario de Síntesis Orgánica
Keywords: Organocatalysis | Aldol reactions | Kinetics | Reaction mechanisms | Transition states
Knowledge Area: Química Orgánica
Issue Date: Apr-2015
Publisher: Wiley-VCH Verlag GmbH & Co. KGaA
Citation: European Journal of Organic Chemistry. 2015, 11: 2503-2516. doi:10.1002/ejoc.201500160
Abstract: The organocatalytic activities of highly substituted proline esters obtained through asymmetric [3+2] cycloadditions of azomethine ylides derived from glycine iminoesters have been analyzed by 19F NMR and through kinetic isotope effects. Kinetic rate constants have been determined for unnatural proline esters incorporating different substituents. It has been found that exo-L and endo-L unnatural proline methyl esters yield opposite enantiomers in aldol reactions between cyclic ketones and aromatic aldehydes. The combined results reported in this study show subtle and remote effects that determine the organocatalytic behavior of these synthetic but readily available amino acid derivatives. These data can be used as design criteria for the development of new pyrrolidine-based organocatalysts.
Sponsor: Financial support was provided by the Spanish Ministerio de Economía y Competitividad (MINECO) and the Fondo Europeo de Desarrollo Regional (FEDER) (projects CTQ2010-16959/BQU, CTQ2012-35535, CTQ2013-40855-R, CTQ2007-62771/BQU, CTQ2010-20387, CTQ2010-17436, and Consolider-Ingenio CSD2007-00006), the University of the Basque Country (UPV/EHU, UFI11/22 QOSYC), the Basque Government (GV/EJ, grant IT-324-07), the Generalitat Valenciana-FEDER (PROMETEO/2009/039), the Gobierno de Aragón-FSE (research group E40), and the University of Alicante. M. d. G. R. thanks the Donostia International Physics Center (DIPC) for a postdoctoral contract. M. S. and L. C. gratefully thank MINECO for a contract funding their PhD projects.
ISSN: 1434-193X (Print) | 1099-0690 (Online)
DOI: 10.1002/ejoc.201500160
Language: eng
Type: info:eu-repo/semantics/article
Rights: © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Peer Review: si
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Appears in Collections:INV - SINTAS - Artículos de Revistas

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