Concentration Effect in the Asymmetric Michael Addition of Acetone to β-Nitrostyrenes Catalyzed by Primary Amine Thioureas

Bifunctional primary amine thiourea (PAT) organocatalysts show remarkable improvement in enantioselectivity and catalytic activity (turnover frequency) in the asymmetric Michael addition of acetone to β-nitrostyrenes upon dilution. Mechanistic investigations indicate that this behavior corresponds t...

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Detalhes bibliográficos
Autores: Günler, Z. Inci, Alfonso, Ignacio, Jimeno, Ciril, Pericàs, Miquel Àngel
Tipo de documento: artigo
Estado:Versión aceptada para publicación
Data de publicação:2017
País:España
Recursos:Consejo Superior de Investigaciones Científicas (CSIC)
Repositório:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/181998
Acesso em linha:http://hdl.handle.net/10261/181998
Access Level:Acceso aberto
Palavra-chave:Enantioselectivity
Aldehydes
Direct aldol
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spelling Concentration Effect in the Asymmetric Michael Addition of Acetone to β-Nitrostyrenes Catalyzed by Primary Amine ThioureasGünler, Z. InciAlfonso, IgnacioJimeno, CirilPericàs, Miquel ÀngelEnantioselectivityAldehydesDirect aldolBifunctional primary amine thiourea (PAT) organocatalysts show remarkable improvement in enantioselectivity and catalytic activity (turnover frequency) in the asymmetric Michael addition of acetone to β-nitrostyrenes upon dilution. Mechanistic investigations indicate that this behavior corresponds to the inhibition of off-cycle catalyst deactivation at low concentration, rather than to the operation of aggregation phenomena at high concentration. Reaction at low concentration (≤0.2 M in β-nitrostyrene) leads to the minimization of catalyst deactivation and, thus, to the optimization of yield and ee of the Michael addition products. © 2011 Published by Elsevier B.V.Financial support from MINECO (Grants CTQ2015-70117-R and CTQ2015-69136-R), Generalitat de Catalunya (Grants 2014SGR231 and 2014SGR827) and the ICIQ Foundation is acknowledged. We also thank MINECO for a Severo Ochoa Excellence Accreditation 2014– 2018 (SEV-2013-0319). C.J. thanks the Ramón y Cajal program (RYC- 2010-06750) for financial support. Z.I.G. holds a FI-DGR predoctoral fellowship (2013FI_B 00395).Peer reviewedThiemeMinisterio de Economía y Competitividad (España)Alfonso, Ignacio [0000-0003-0678-0362]Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]201920192017info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Postprintinfo:eu-repo/semantics/acceptedVersionhttp://hdl.handle.net/10261/181998reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Inglés#PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE#info:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2015-70117-Rinfo:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2015-69136-R10.1055/s-0036-1589408Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/1819982026-05-22T06:33:51Z
dc.title.none.fl_str_mv Concentration Effect in the Asymmetric Michael Addition of Acetone to β-Nitrostyrenes Catalyzed by Primary Amine Thioureas
title Concentration Effect in the Asymmetric Michael Addition of Acetone to β-Nitrostyrenes Catalyzed by Primary Amine Thioureas
spellingShingle Concentration Effect in the Asymmetric Michael Addition of Acetone to β-Nitrostyrenes Catalyzed by Primary Amine Thioureas
Günler, Z. Inci
Enantioselectivity
Aldehydes
Direct aldol
title_short Concentration Effect in the Asymmetric Michael Addition of Acetone to β-Nitrostyrenes Catalyzed by Primary Amine Thioureas
title_full Concentration Effect in the Asymmetric Michael Addition of Acetone to β-Nitrostyrenes Catalyzed by Primary Amine Thioureas
title_fullStr Concentration Effect in the Asymmetric Michael Addition of Acetone to β-Nitrostyrenes Catalyzed by Primary Amine Thioureas
title_full_unstemmed Concentration Effect in the Asymmetric Michael Addition of Acetone to β-Nitrostyrenes Catalyzed by Primary Amine Thioureas
title_sort Concentration Effect in the Asymmetric Michael Addition of Acetone to β-Nitrostyrenes Catalyzed by Primary Amine Thioureas
dc.creator.none.fl_str_mv Günler, Z. Inci
Alfonso, Ignacio
Jimeno, Ciril
Pericàs, Miquel Àngel
author Günler, Z. Inci
author_facet Günler, Z. Inci
Alfonso, Ignacio
Jimeno, Ciril
Pericàs, Miquel Àngel
author_role author
author2 Alfonso, Ignacio
Jimeno, Ciril
Pericàs, Miquel Àngel
author2_role author
author
author
dc.contributor.none.fl_str_mv Ministerio de Economía y Competitividad (España)
Alfonso, Ignacio [0000-0003-0678-0362]
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
dc.subject.none.fl_str_mv Enantioselectivity
Aldehydes
Direct aldol
topic Enantioselectivity
Aldehydes
Direct aldol
description Bifunctional primary amine thiourea (PAT) organocatalysts show remarkable improvement in enantioselectivity and catalytic activity (turnover frequency) in the asymmetric Michael addition of acetone to β-nitrostyrenes upon dilution. Mechanistic investigations indicate that this behavior corresponds to the inhibition of off-cycle catalyst deactivation at low concentration, rather than to the operation of aggregation phenomena at high concentration. Reaction at low concentration (≤0.2 M in β-nitrostyrene) leads to the minimization of catalyst deactivation and, thus, to the optimization of yield and ee of the Michael addition products. © 2011 Published by Elsevier B.V.
publishDate 2017
dc.date.none.fl_str_mv 2017
2019
2019
dc.type.none.fl_str_mv info:eu-repo/semantics/article
http://purl.org/coar/resource_type/c_6501
Postprint
info:eu-repo/semantics/acceptedVersion
format article
status_str acceptedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10261/181998
url http://hdl.handle.net/10261/181998
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv #PLACEHOLDER_PARENT_METADATA_VALUE#
#PLACEHOLDER_PARENT_METADATA_VALUE#
info:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2015-70117-R
info:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2015-69136-R
10.1055/s-0036-1589408
Sí
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.publisher.none.fl_str_mv Thieme
publisher.none.fl_str_mv Thieme
dc.source.none.fl_str_mv reponame:DIGITAL.CSIC. Repositorio Institucional del CSIC
instname:Consejo Superior de Investigaciones Científicas (CSIC)
instname_str Consejo Superior de Investigaciones Científicas (CSIC)
reponame_str DIGITAL.CSIC. Repositorio Institucional del CSIC
collection DIGITAL.CSIC. Repositorio Institucional del CSIC
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