Comprehensive Mechanistic Scenario for the Cu-Mediated Asymmetric Propargylic Sulfonylation Forging Tertiary Carbon Stereocenters

Metal-catalyzed propargylic transformations represent a powerful tool in organic synthesis to achieve new carbon–carbon and carbon–heteroatom bonds. However, detailed knowledge about the mechanistic intricacies related to the asymmetric formation of propargylic products featuring challenging heteroa...

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Autores: Garcia-Roca, Aleria, Pérez-Soto, Raúl, Stoica, Georgiana, Benet-Buchholz, Jordi, Maseras, Feliu, Kleij, Arjan W.
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2023
País:España
Institución:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
Repositorio:Recercat. Dipósit de la Recerca de Catalunya
OAI Identifier:oai:recercat.cat:2072/532932
Acceso en línea:http://hdl.handle.net/2072/532932
https://doi.org/10.1021/jacs.3c00188
Access Level:acceso abierto
Palabra clave:Química
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spelling Comprehensive Mechanistic Scenario for the Cu-Mediated Asymmetric Propargylic Sulfonylation Forging Tertiary Carbon StereocentersGarcia-Roca, AleriaPérez-Soto, RaúlStoica, GeorgianaBenet-Buchholz, JordiMaseras, FeliuKleij, Arjan W.Química00Metal-catalyzed propargylic transformations represent a powerful tool in organic synthesis to achieve new carbon–carbon and carbon–heteroatom bonds. However, detailed knowledge about the mechanistic intricacies related to the asymmetric formation of propargylic products featuring challenging heteroatom-substituted tertiary stereocenters is scarce and therefore provides an inspiring challenge. Here, we present a meticulous mechanistic analysis of a propargylic sulfonylation reaction promoted by a chiral Cu catalyst through a combination of experimental techniques and computational studies. Surprisingly, the enantio-discriminating step is not the coupling between the nucleophile and the propargylic precursor but rather the following proto-demetalation step, a scenario further validated by computing enantio-induction levels under other previously reported experimental conditions. A full mechanistic scenario for this propargylic substitution reaction is provided, including a catalyst pre-activation stage, a productive catalytic cycle, and an unanticipated non-linear effect at the Cu(I) oxidation level.ACS Publications2023info:eu-repo/semantics/articleinfo:eu-repo/semantics/acceptedVersion13 p.application/pdfhttp://hdl.handle.net/2072/532932https://doi.org/10.1021/jacs.3c00188RECERCAT (Dipòsit de la Recerca de Catalunya)reponame:Recercat. Dipósit de la Recerca de Catalunyainstname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)InglésCerca program/Generalitat de CatalunyaICREAMICINN (PID2020-112684GB-I00, PID2020-112825RB-100, Severo Ochoa Excellence Accreditation 2020−2023 CEX2019-000925-S)Ministerio de Universidades for a predoctoral fellowship (FPU18/01138)Creative Commons Attribution-NonCommercial-NoDerivs Licenseinfo:eu-repo/semantics/openAccessoai:recercat.cat:2072/5329322026-05-29T05:05:01Z
dc.title.none.fl_str_mv Comprehensive Mechanistic Scenario for the Cu-Mediated Asymmetric Propargylic Sulfonylation Forging Tertiary Carbon Stereocenters
title Comprehensive Mechanistic Scenario for the Cu-Mediated Asymmetric Propargylic Sulfonylation Forging Tertiary Carbon Stereocenters
spellingShingle Comprehensive Mechanistic Scenario for the Cu-Mediated Asymmetric Propargylic Sulfonylation Forging Tertiary Carbon Stereocenters
Garcia-Roca, Aleria
Química
00
title_short Comprehensive Mechanistic Scenario for the Cu-Mediated Asymmetric Propargylic Sulfonylation Forging Tertiary Carbon Stereocenters
title_full Comprehensive Mechanistic Scenario for the Cu-Mediated Asymmetric Propargylic Sulfonylation Forging Tertiary Carbon Stereocenters
title_fullStr Comprehensive Mechanistic Scenario for the Cu-Mediated Asymmetric Propargylic Sulfonylation Forging Tertiary Carbon Stereocenters
title_full_unstemmed Comprehensive Mechanistic Scenario for the Cu-Mediated Asymmetric Propargylic Sulfonylation Forging Tertiary Carbon Stereocenters
title_sort Comprehensive Mechanistic Scenario for the Cu-Mediated Asymmetric Propargylic Sulfonylation Forging Tertiary Carbon Stereocenters
dc.creator.none.fl_str_mv Garcia-Roca, Aleria
Pérez-Soto, Raúl
Stoica, Georgiana
Benet-Buchholz, Jordi
Maseras, Feliu
Kleij, Arjan W.
author Garcia-Roca, Aleria
author_facet Garcia-Roca, Aleria
Pérez-Soto, Raúl
Stoica, Georgiana
Benet-Buchholz, Jordi
Maseras, Feliu
Kleij, Arjan W.
author_role author
author2 Pérez-Soto, Raúl
Stoica, Georgiana
Benet-Buchholz, Jordi
Maseras, Feliu
Kleij, Arjan W.
author2_role author
author
author
author
author
dc.subject.none.fl_str_mv Química
00
topic Química
00
description Metal-catalyzed propargylic transformations represent a powerful tool in organic synthesis to achieve new carbon–carbon and carbon–heteroatom bonds. However, detailed knowledge about the mechanistic intricacies related to the asymmetric formation of propargylic products featuring challenging heteroatom-substituted tertiary stereocenters is scarce and therefore provides an inspiring challenge. Here, we present a meticulous mechanistic analysis of a propargylic sulfonylation reaction promoted by a chiral Cu catalyst through a combination of experimental techniques and computational studies. Surprisingly, the enantio-discriminating step is not the coupling between the nucleophile and the propargylic precursor but rather the following proto-demetalation step, a scenario further validated by computing enantio-induction levels under other previously reported experimental conditions. A full mechanistic scenario for this propargylic substitution reaction is provided, including a catalyst pre-activation stage, a productive catalytic cycle, and an unanticipated non-linear effect at the Cu(I) oxidation level.
publishDate 2023
dc.date.none.fl_str_mv 2023
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/acceptedVersion
format article
status_str acceptedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/2072/532932
https://doi.org/10.1021/jacs.3c00188
url http://hdl.handle.net/2072/532932
https://doi.org/10.1021/jacs.3c00188
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv Cerca program/Generalitat de Catalunya
ICREA
MICINN (PID2020-112684GB-I00, PID2020-112825RB-100, Severo Ochoa Excellence Accreditation 2020−2023 CEX2019-000925-S)
Ministerio de Universidades for a predoctoral fellowship (FPU18/01138)
dc.rights.none.fl_str_mv Creative Commons Attribution-NonCommercial-NoDerivs License
info:eu-repo/semantics/openAccess
rights_invalid_str_mv Creative Commons Attribution-NonCommercial-NoDerivs License
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv 13 p.
application/pdf
dc.publisher.none.fl_str_mv ACS Publications
publisher.none.fl_str_mv ACS Publications
dc.source.none.fl_str_mv RECERCAT (Dipòsit de la Recerca de Catalunya)
reponame:Recercat. Dipósit de la Recerca de Catalunya
instname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
instname_str Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
reponame_str Recercat. Dipósit de la Recerca de Catalunya
collection Recercat. Dipósit de la Recerca de Catalunya
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15.812429

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