syn-Selective Michael reaction of α-branched aryl acetaldehydes with nitroolefins promoted by squaric amino acid derived bifunctional Brønsted bases

[EN] Here we describe a direct access to 2,2,3-trisubstituted syn γ-nitroaldehydes by addition of α-branched aryl acetaldehydes to nitroolefins promoted by a cinchona based squaric acid-derived amino acid peptide. Different α-methyl arylacetaldehydes react with β-aromatic and β-alkyl nitroolefins to...

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Autores: García Urricelqui, Ane, De Cózar Ruano, Abel, Campano García, Teresa Esperanza, Mielgo Vicente, María Antonia, Palomo Nicolau, Claudio
Tipo de recurso: artículo
Fecha de publicación:2021
País:España
Institución:Universidad del País Vasco
Repositorio:Addi. Archivo Digital para la Docencia y la Investigación
OAI Identifier:oai:addi.ehu.eus:10810/52893
Acceso en línea:http://hdl.handle.net/10810/52893
Access Level:acceso abierto
Palabra clave:α-branched arylacetaldehydes
Brønsted bases
Michael reaction
nitroolefins
organocatalysis
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spelling syn-Selective Michael reaction of α-branched aryl acetaldehydes with nitroolefins promoted by squaric amino acid derived bifunctional Brønsted basesGarcía Urricelqui, AneDe Cózar Ruano, AbelCampano García, Teresa EsperanzaMielgo Vicente, María AntoniaPalomo Nicolau, Claudioα-branched arylacetaldehydesBrønsted basesMichael reactionnitroolefinsorganocatalysis[EN] Here we describe a direct access to 2,2,3-trisubstituted syn γ-nitroaldehydes by addition of α-branched aryl acetaldehydes to nitroolefins promoted by a cinchona based squaric acid-derived amino acid peptide. Different α-methyl arylacetaldehydes react with β-aromatic and β-alkyl nitroolefins to afford the Michael adducts in high enantioselectivity and syn-selectivity. NMR experiments and DFT calculations predict the reaction to occur through the intermediacy of E-enolate. The interaction between the substrates and the catalyst follows Pápai’s model, wherein an intramolecular H-bond interaction in the catalyst between the NH group of one of the tert-leucines and the squaramide oxygen seems to be key for discrimination of the corresponding reaction transition states.Support has been provided by the University of the Basque Country UPV/EHU (UFI QOSYC 11/22), Basque Government (GV grant IT1236-19), and Ministerio de Ciencia e Innovación (grant PID2019-109633GB-C21), Spain. A. G. and T. E. thank Basque Government and MINECO respectively for fellowships. We would like to express our gratitude to the students I. Gonzalez-Mujika and M. Campo for their participation in conducting some experiments of the reaction scope. We also thank SGIker (UPV/EHU) for providing NMR, HRMS. X-Ray and computational resources.Wiley202120212021info:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10810/52893reponame:Addi. Archivo Digital para la Docencia y la Investigacióninstname:Universidad del País VascoInglésinfo:eu-repo/grantAgreement/MINECO/PID2019-109633GB-C21/https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/ejoc.202100355info:eu-repo/semantics/openAccesshttp://creativecommons.org/licenses/by-nc-nd/3.0/es/© 2021 The Authors. European Journal of Organic Chemistry published by Wiley-VCH GmbH. This is an open access article under the terms of the Creative Commons Attribution Non-Commercial NoDerivs License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non-commercial and no modifications or adaptations are made. (CC by-nc-nd)Atribución-NoComercial-SinDerivadas 3.0 Españaoai:addi.ehu.eus:10810/528932026-06-18T09:23:17Z
dc.title.none.fl_str_mv syn-Selective Michael reaction of α-branched aryl acetaldehydes with nitroolefins promoted by squaric amino acid derived bifunctional Brønsted bases
title syn-Selective Michael reaction of α-branched aryl acetaldehydes with nitroolefins promoted by squaric amino acid derived bifunctional Brønsted bases
spellingShingle syn-Selective Michael reaction of α-branched aryl acetaldehydes with nitroolefins promoted by squaric amino acid derived bifunctional Brønsted bases
García Urricelqui, Ane
α-branched arylacetaldehydes
Brønsted bases
Michael reaction
nitroolefins
organocatalysis
title_short syn-Selective Michael reaction of α-branched aryl acetaldehydes with nitroolefins promoted by squaric amino acid derived bifunctional Brønsted bases
title_full syn-Selective Michael reaction of α-branched aryl acetaldehydes with nitroolefins promoted by squaric amino acid derived bifunctional Brønsted bases
title_fullStr syn-Selective Michael reaction of α-branched aryl acetaldehydes with nitroolefins promoted by squaric amino acid derived bifunctional Brønsted bases
title_full_unstemmed syn-Selective Michael reaction of α-branched aryl acetaldehydes with nitroolefins promoted by squaric amino acid derived bifunctional Brønsted bases
title_sort syn-Selective Michael reaction of α-branched aryl acetaldehydes with nitroolefins promoted by squaric amino acid derived bifunctional Brønsted bases
dc.creator.none.fl_str_mv García Urricelqui, Ane
De Cózar Ruano, Abel
Campano García, Teresa Esperanza
Mielgo Vicente, María Antonia
Palomo Nicolau, Claudio
author García Urricelqui, Ane
author_facet García Urricelqui, Ane
De Cózar Ruano, Abel
Campano García, Teresa Esperanza
Mielgo Vicente, María Antonia
Palomo Nicolau, Claudio
author_role author
author2 De Cózar Ruano, Abel
Campano García, Teresa Esperanza
Mielgo Vicente, María Antonia
Palomo Nicolau, Claudio
author2_role author
author
author
author
dc.subject.none.fl_str_mv α-branched arylacetaldehydes
Brønsted bases
Michael reaction
nitroolefins
organocatalysis
topic α-branched arylacetaldehydes
Brønsted bases
Michael reaction
nitroolefins
organocatalysis
description [EN] Here we describe a direct access to 2,2,3-trisubstituted syn γ-nitroaldehydes by addition of α-branched aryl acetaldehydes to nitroolefins promoted by a cinchona based squaric acid-derived amino acid peptide. Different α-methyl arylacetaldehydes react with β-aromatic and β-alkyl nitroolefins to afford the Michael adducts in high enantioselectivity and syn-selectivity. NMR experiments and DFT calculations predict the reaction to occur through the intermediacy of E-enolate. The interaction between the substrates and the catalyst follows Pápai’s model, wherein an intramolecular H-bond interaction in the catalyst between the NH group of one of the tert-leucines and the squaramide oxygen seems to be key for discrimination of the corresponding reaction transition states.
publishDate 2021
dc.date.none.fl_str_mv 2021
2021
2021
dc.type.none.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv http://hdl.handle.net/10810/52893
url http://hdl.handle.net/10810/52893
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv info:eu-repo/grantAgreement/MINECO/PID2019-109633GB-C21/
https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/ejoc.202100355
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
http://creativecommons.org/licenses/by-nc-nd/3.0/es/
Atribución-NoComercial-SinDerivadas 3.0 España
eu_rights_str_mv openAccess
rights_invalid_str_mv http://creativecommons.org/licenses/by-nc-nd/3.0/es/
Atribución-NoComercial-SinDerivadas 3.0 España
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv Wiley
publisher.none.fl_str_mv Wiley
dc.source.none.fl_str_mv reponame:Addi. Archivo Digital para la Docencia y la Investigación
instname:Universidad del País Vasco
instname_str Universidad del País Vasco
reponame_str Addi. Archivo Digital para la Docencia y la Investigación
collection Addi. Archivo Digital para la Docencia y la Investigación
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15,300724

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