Heterocycle-based bifunctional organocatalysts in asymmetric synthesis

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Title: Heterocycle-based bifunctional organocatalysts in asymmetric synthesis
Authors: Nájera, Carmen | Sansano, Jose M. | Gómez Bengoa, Enrique
Research Group/s: Síntesis Asimétrica (SINTAS)
Center, Department or Service: Universidad de Alicante. Departamento de Química Orgánica
Keywords: Aldols | Asymmetric synthesis | Bifunctional catalysis | Carbenium ions | 1,3-dicarbonyl compounds | Hydrogen bonding | Nitro compounds | Succinimides | TRAMECH VIII
Knowledge Area: Química Orgánica
Issue Date: 28-Jul-2016
Publisher: De Gruyter
Citation: Pure and Applied Chemistry. 2016, 88(6): 561-578. doi:10.1515/pac-2016-0403
Abstract: Different chiral bifunctional organocatalysts derived from trans-cyclohexane-1,2-diamine bearing different types of guanidine units able to form-hydrogen bonding activation have been designed. Conformational rigid 2-aminobenzimidazoles bearing a tertiary amino group have been used in enantioselective Michael type reactions of activated methylene compounds to nitroalkenes. The C2 symmetric bis(2-aminobenzimidazole) derivatives the appropriate organocatalyst for the conjugate addition of 1,3-dicarbonyl compounds to maleimides as well as for the SN1 reaction of benzylic alcohols with carbon nucleophiles. 2-Aminobenzimidazoles bearing a primary amino group have shown excellent catalytic activity in the Michael reaction of aldehydes to maleimides and nitroalkenes. Diastereomeric 2-aminopyrimidines bearing a prolinamide unit have been incorporated in the trans-cyclohexane-1,2-diamine scaffold and have been used for the inter- and intra-molecular direct aldol reaction under solvent-free conditions. For the Michael reaction of aldehydes with maleimides the primary amine 2-aminopyrimidine has shown excellent efficiency as organocatalyst. The bifunctional character of these organocatalysts has been demonstrated by means of DFT calculations.
Sponsor: The Spanish Ministerio de Ciencia e Innovación (MICINN) (projects CTQ2010-20387, and Consolider Ingenio 2010, CSD2007-00006), the Spanish Ministerio de Economía y Competitividad (MINECO) (projects CTQ2013-43446-P and CTQ2014-51912-REDC), FEDER, the Generalitat Valenciana (PROMETEO 2009/039 and PROMETEOII/2014/017), the Basque Government (GV Grant IT-291-07), the FP7 Marie Curie Actions of the European Commission via the ITN ECHONET network (MCITN-2012-316379) and the Universities of Alicante and Basque Country are gratefully acknowledged for financial support. We also thank for technical and human support provided by IZO-SGI SGIker of UPV-EHU and European funding (ERDF and ESF).
URI: http://hdl.handle.net/10045/59654
ISSN: 0033-4545 (Print) | 1365-3075 (Online)
DOI: 10.1515/pac-2016-0403
Language: eng
Type: info:eu-repo/semantics/article
Rights: © 2016 IUPAC & De Gruyter. This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License. For more information, please visit: http://creativecommons.org/licenses/by-nc-nd/4.0/
Peer Review: si
Publisher version: http://dx.doi.org/10.1515/pac-2016-0403
Appears in Collections:INV - SINTAS - Artículos de Revistas
Research funded by the EU

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