Origin of the Felkin-Anh(-Eisenstein) Model: a Quantitative Rationalization of a Seminal Concept

Quantum chemical calculations were carried out to quantitatively understand the origin of the Felkin–Anh(–Eisenstein) model, widely used to rationalize the π-facial stereoselectivity in the nucleophilic addition reaction to carbonyl groups directly attached to a stereogenic center. To this end, the...

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Autores: González Pinardo, Daniel, Bickelhaupt, F. Matthias, Fernández López, Israel
Tipo de recurso: artículo
Fecha de publicación:2024
País:España
Institución:Universidad Complutense de Madrid (UCM)
Repositorio:Docta Complutense
Idioma:inglés
OAI Identifier:oai:docta.ucm.es:20.500.14352/109214
Acceso en línea:https://hdl.handle.net/20.500.14352/109214
Access Level:acceso abierto
Palabra clave:Química orgánica (Química)
2306 Química Orgánica
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spelling Origin of the Felkin-Anh(-Eisenstein) Model: a Quantitative Rationalization of a Seminal ConceptGonzález Pinardo, DanielBickelhaupt, F. MatthiasFernández López, IsraelQuímica orgánica (Química)2306 Química OrgánicaQuantum chemical calculations were carried out to quantitatively understand the origin of the Felkin–Anh(–Eisenstein) model, widely used to rationalize the π-facial stereoselectivity in the nucleophilic addition reaction to carbonyl groups directly attached to a stereogenic center. To this end, the possible approaches of cyanide to both (S)-2-phenylpropanal and (S)-3-phenylbutan-2-one have been explored in detail. With the help of the activation strain model of reactivity and the energy decomposition analysis method, it is found that the preference for the Felkin–Anh addition is mainly dictated by steric factors which manifest in a less destabilizing strain-energy rather than, as traditionally considered, in a lower Pauli repulsion. In addition, other factors such as the more favorable electrostatic interactions also contribute to the preferred approach of the nucleophile. Our work, therefore, provides a different, more complete rationalization, based on quantitative analyses, of the origin of this seminal and highly useful concept in organic chemistry.Royal Society of ChemistryUniversidad Complutense de Madrid20242024-01-0120242024-01-01journal articlehttp://purl.org/coar/resource_type/c_6501VoRhttp://purl.org/coar/version/c_970fb48d4fbd8a85info:eu-repo/semantics/articleapplication/pdfhttps://hdl.handle.net/20.500.14352/109214reponame:Docta Complutenseinstname:Universidad Complutense de Madrid (UCM)InglésengMCIN%AEI%10.13039%501100011033 PID2022-139318NB-I00 Not availableMCIN%AEI%10.13039%501100011033 RED2022-134287-T Not availableopen accesshttp://purl.org/coar/access_right/c_abf2Attribution 4.0 Internationalhttp://creativecommons.org/licenses/by/4.0/info:eu-repo/semantics/openAccessoai:docta.ucm.es:20.500.14352/1092142026-06-02T12:44:21Z
dc.title.none.fl_str_mv Origin of the Felkin-Anh(-Eisenstein) Model: a Quantitative Rationalization of a Seminal Concept
title Origin of the Felkin-Anh(-Eisenstein) Model: a Quantitative Rationalization of a Seminal Concept
spellingShingle Origin of the Felkin-Anh(-Eisenstein) Model: a Quantitative Rationalization of a Seminal Concept
González Pinardo, Daniel
Química orgánica (Química)
2306 Química Orgánica
title_short Origin of the Felkin-Anh(-Eisenstein) Model: a Quantitative Rationalization of a Seminal Concept
title_full Origin of the Felkin-Anh(-Eisenstein) Model: a Quantitative Rationalization of a Seminal Concept
title_fullStr Origin of the Felkin-Anh(-Eisenstein) Model: a Quantitative Rationalization of a Seminal Concept
title_full_unstemmed Origin of the Felkin-Anh(-Eisenstein) Model: a Quantitative Rationalization of a Seminal Concept
title_sort Origin of the Felkin-Anh(-Eisenstein) Model: a Quantitative Rationalization of a Seminal Concept
dc.creator.none.fl_str_mv González Pinardo, Daniel
Bickelhaupt, F. Matthias
Fernández López, Israel
author González Pinardo, Daniel
author_facet González Pinardo, Daniel
Bickelhaupt, F. Matthias
Fernández López, Israel
author_role author
author2 Bickelhaupt, F. Matthias
Fernández López, Israel
author2_role author
author
dc.contributor.none.fl_str_mv Universidad Complutense de Madrid
dc.subject.none.fl_str_mv Química orgánica (Química)
2306 Química Orgánica
topic Química orgánica (Química)
2306 Química Orgánica
description Quantum chemical calculations were carried out to quantitatively understand the origin of the Felkin–Anh(–Eisenstein) model, widely used to rationalize the π-facial stereoselectivity in the nucleophilic addition reaction to carbonyl groups directly attached to a stereogenic center. To this end, the possible approaches of cyanide to both (S)-2-phenylpropanal and (S)-3-phenylbutan-2-one have been explored in detail. With the help of the activation strain model of reactivity and the energy decomposition analysis method, it is found that the preference for the Felkin–Anh addition is mainly dictated by steric factors which manifest in a less destabilizing strain-energy rather than, as traditionally considered, in a lower Pauli repulsion. In addition, other factors such as the more favorable electrostatic interactions also contribute to the preferred approach of the nucleophile. Our work, therefore, provides a different, more complete rationalization, based on quantitative analyses, of the origin of this seminal and highly useful concept in organic chemistry.
publishDate 2024
dc.date.none.fl_str_mv 2024
2024-01-01
2024
2024-01-01
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/20.500.14352/109214
url https://hdl.handle.net/20.500.14352/109214
dc.language.none.fl_str_mv Inglés
eng
language_invalid_str_mv Inglés
language eng
dc.relation.none.fl_str_mv MCIN%AEI%10.13039%501100011033 PID2022-139318NB-I00 Not available
MCIN%AEI%10.13039%501100011033 RED2022-134287-T Not available
dc.rights.none.fl_str_mv open access
http://purl.org/coar/access_right/c_abf2
Attribution 4.0 International
http://creativecommons.org/licenses/by/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 4.0 International
http://creativecommons.org/licenses/by/4.0/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv Royal Society of Chemistry
publisher.none.fl_str_mv Royal Society of Chemistry
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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