How dihalogens catalyze michael addition reactions

We have quantum chemically analyzed the catalytic effect of dihalogen molecules (X2 = F2, Cl2 , Br2, and I2) on the aza-Michael addition of pyrrolidine and methyl acrylate using relativistic density functional theory and coupled-cluster theory. Our state-of-the-art computations reveal that activatio...

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Detalles Bibliográficos
Autores: Hamlin, Trevor, Fernández López, Israel, Bickelhaupt, Matthias
Tipo de recurso: artículo
Fecha de publicación:2019
País:España
Institución:Universidad Complutense de Madrid (UCM)
Repositorio:Docta Complutense
Idioma:inglés
OAI Identifier:oai:docta.ucm.es:20.500.14352/101611
Acceso en línea:https://hdl.handle.net/20.500.14352/101611
Access Level:acceso abierto
Palabra clave:547
Química orgánica (Química)
2306 Química Orgánica
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oai_identifier_str oai:docta.ucm.es:20.500.14352/101611
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spelling How dihalogens catalyze michael addition reactionsHamlin, TrevorFernández López, IsraelBickelhaupt, Matthias547Química orgánica (Química)2306 Química OrgánicaWe have quantum chemically analyzed the catalytic effect of dihalogen molecules (X2 = F2, Cl2 , Br2, and I2) on the aza-Michael addition of pyrrolidine and methyl acrylate using relativistic density functional theory and coupled-cluster theory. Our state-of-the-art computations reveal that activation barriers systematically decrease as one goes to heavier dihalogens, from 9.4 kcalmol@1 for F2 to 5.7 kcalmol@1 for I2. Activation strain and bonding analyses identify an unexpected physical factor that controls the computed reactivity trends, namely, Pauli repulsion between the nucleophile and Michael acceptor. Thus, dihalogens do not accelerate Michael additions by the commonly accepted mechanism of an enhanced donor– acceptor [HOMO(nucleophile) LUMO(Michael acceptor)] interaction, but instead through a diminished Pauli repulsion between the lone-pair of the nucleophile and the Michael acceptorQs p-electron system.WileyUniversidad Complutense de Madrid20192019-01-0120192019-01-01journal articlehttp://purl.org/coar/resource_type/c_6501VoRhttp://purl.org/coar/version/c_970fb48d4fbd8a85info:eu-repo/semantics/articleapplication/pdfhttps://hdl.handle.net/20.500.14352/101611reponame:Docta Complutenseinstname:Universidad Complutense de Madrid (UCM)Inglésengopen accesshttp://purl.org/coar/access_right/c_abf2Attribution-NonCommercial-NoDerivatives 4.0 Internationalhttp://creativecommons.org/licenses/by-nc-nd/4.0/info:eu-repo/semantics/openAccessoai:docta.ucm.es:20.500.14352/1016112026-06-02T12:44:21Z
dc.title.none.fl_str_mv How dihalogens catalyze michael addition reactions
title How dihalogens catalyze michael addition reactions
spellingShingle How dihalogens catalyze michael addition reactions
Hamlin, Trevor
547
Química orgánica (Química)
2306 Química Orgánica
title_short How dihalogens catalyze michael addition reactions
title_full How dihalogens catalyze michael addition reactions
title_fullStr How dihalogens catalyze michael addition reactions
title_full_unstemmed How dihalogens catalyze michael addition reactions
title_sort How dihalogens catalyze michael addition reactions
dc.creator.none.fl_str_mv Hamlin, Trevor
Fernández López, Israel
Bickelhaupt, Matthias
author Hamlin, Trevor
author_facet Hamlin, Trevor
Fernández López, Israel
Bickelhaupt, Matthias
author_role author
author2 Fernández López, Israel
Bickelhaupt, Matthias
author2_role author
author
dc.contributor.none.fl_str_mv Universidad Complutense de Madrid
dc.subject.none.fl_str_mv 547
Química orgánica (Química)
2306 Química Orgánica
topic 547
Química orgánica (Química)
2306 Química Orgánica
description We have quantum chemically analyzed the catalytic effect of dihalogen molecules (X2 = F2, Cl2 , Br2, and I2) on the aza-Michael addition of pyrrolidine and methyl acrylate using relativistic density functional theory and coupled-cluster theory. Our state-of-the-art computations reveal that activation barriers systematically decrease as one goes to heavier dihalogens, from 9.4 kcalmol@1 for F2 to 5.7 kcalmol@1 for I2. Activation strain and bonding analyses identify an unexpected physical factor that controls the computed reactivity trends, namely, Pauli repulsion between the nucleophile and Michael acceptor. Thus, dihalogens do not accelerate Michael additions by the commonly accepted mechanism of an enhanced donor– acceptor [HOMO(nucleophile) LUMO(Michael acceptor)] interaction, but instead through a diminished Pauli repulsion between the lone-pair of the nucleophile and the Michael acceptorQs p-electron system.
publishDate 2019
dc.date.none.fl_str_mv 2019
2019-01-01
2019
2019-01-01
dc.type.none.fl_str_mv journal article
http://purl.org/coar/resource_type/c_6501
VoR
http://purl.org/coar/version/c_970fb48d4fbd8a85
dc.type.openaire.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv https://hdl.handle.net/20.500.14352/101611
url https://hdl.handle.net/20.500.14352/101611
dc.language.none.fl_str_mv Inglés
eng
language_invalid_str_mv Inglés
language eng
dc.rights.none.fl_str_mv open access
http://purl.org/coar/access_right/c_abf2
Attribution-NonCommercial-NoDerivatives 4.0 International
http://creativecommons.org/licenses/by-nc-nd/4.0/
dc.rights.openaire.fl_str_mv info:eu-repo/semantics/openAccess
rights_invalid_str_mv open access
http://purl.org/coar/access_right/c_abf2
Attribution-NonCommercial-NoDerivatives 4.0 International
http://creativecommons.org/licenses/by-nc-nd/4.0/
eu_rights_str_mv openAccess
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:Docta Complutense
instname:Universidad Complutense de Madrid (UCM)
instname_str Universidad Complutense de Madrid (UCM)
reponame_str Docta Complutense
collection Docta Complutense
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15,300724

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