Well-Defined β-Diketiminatocobalt(II) Complexes for Alkene Cyclohydroamination of Primary Amines

A well-defined low-coordinate β-diketiminatocobalt(II) alkyl complex is reported as an active precatalyst for the selective alkene cyclohydroamination of unprotected primary amines under mild conditions (rt-90 °C). The reaction mechanism has been investigated by deuterium-labeling, kinetics, and sto...

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Autores: Lepori, Clément, Gómez-Orellana Seguín, Pablo|||0000-0001-6068-7711, Ouharzoune, Allissa, Guillot, Régis, Lledós, Agustí|||0000-0001-7909-422X, Ujaque, Gregori|||0000-0001-5896-9998, Hannedouche, Jérôme
Tipo de recurso: artículo
Fecha de publicación:2018
País:España
Institución:Universitat Autònoma de Barcelona
Repositorio:Dipòsit Digital de Documents de la UAB
Idioma:inglés
OAI Identifier:oai:ddd.uab.cat:279261
Acceso en línea:https://ddd.uab.cat/record/279261
https://dx.doi.org/urn:doi:10.1021/acscatal.8b00631
Access Level:acceso abierto
Palabra clave:DFT calculations
Alkenes
Cobalt
Hydroamination
Mechanistic studies
Primary amines
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spelling Well-Defined β-Diketiminatocobalt(II) Complexes for Alkene Cyclohydroamination of Primary AminesLepori, ClémentGómez-Orellana Seguín, Pablo|||0000-0001-6068-7711Ouharzoune, AllissaGuillot, RégisLledós, Agustí|||0000-0001-7909-422XUjaque, Gregori|||0000-0001-5896-9998Hannedouche, JérômeDFT calculationsAlkenesCobaltHydroaminationMechanistic studiesPrimary aminesA well-defined low-coordinate β-diketiminatocobalt(II) alkyl complex is reported as an active precatalyst for the selective alkene cyclohydroamination of unprotected primary amines under mild conditions (rt-90 °C). The reaction mechanism has been investigated by deuterium-labeling, kinetics, and stoichiometric experiments and in-depth computational DFT studies. On the basis of these studies, we propose a stepwise noninsertive mechanism that features a rate-determining nucleophilic attack of the amido group of a monomeric cobalt(II) amidoalkene-aminoalkene adduct intermediate to the noncoordinated pendant alkene followed by a rapid proton transfer from the coordinated aminoalkene to the cyclized adduct. 22018-01-0120182018-01-01Articlehttp://purl.org/coar/resource_type/c_6501AMhttp://purl.org/coar/version/c_ab4af688f83e57aainfo:eu-repo/semantics/articleapplication/pdfhttps://ddd.uab.cat/record/279261https://dx.doi.org/urn:doi:10.1021/acscatal.8b00631reponame:Dipòsit Digital de Documents de la UABinstname:Universitat Autònoma de BarcelonaInglésengAgencia Estatal de Investigación https://doi.org/10.13039/501100011033 CTQ2017-87889-PMinisterio de Economía y Competitividad https://doi.org/10.13039/501100003329 CTQ2016-81797-REDCopen accesshttp://purl.org/coar/access_right/c_abf2Aquest material està protegit per drets d'autor i/o drets afins. Podeu utilitzar aquest material en funció del que permet la legislació de drets d'autor i drets afins d'aplicació al vostre cas. Per a d'altres usos heu d'obtenir permís del(s) titular(s) de drets.https://rightsstatements.org/vocab/InC/1.0/info:eu-repo/semantics/openAccessoai:ddd.uab.cat:2792612026-06-06T12:50:31Z
dc.title.none.fl_str_mv Well-Defined β-Diketiminatocobalt(II) Complexes for Alkene Cyclohydroamination of Primary Amines
title Well-Defined β-Diketiminatocobalt(II) Complexes for Alkene Cyclohydroamination of Primary Amines
spellingShingle Well-Defined β-Diketiminatocobalt(II) Complexes for Alkene Cyclohydroamination of Primary Amines
Lepori, Clément
DFT calculations
Alkenes
Cobalt
Hydroamination
Mechanistic studies
Primary amines
title_short Well-Defined β-Diketiminatocobalt(II) Complexes for Alkene Cyclohydroamination of Primary Amines
title_full Well-Defined β-Diketiminatocobalt(II) Complexes for Alkene Cyclohydroamination of Primary Amines
title_fullStr Well-Defined β-Diketiminatocobalt(II) Complexes for Alkene Cyclohydroamination of Primary Amines
title_full_unstemmed Well-Defined β-Diketiminatocobalt(II) Complexes for Alkene Cyclohydroamination of Primary Amines
title_sort Well-Defined β-Diketiminatocobalt(II) Complexes for Alkene Cyclohydroamination of Primary Amines
dc.creator.none.fl_str_mv Lepori, Clément
Gómez-Orellana Seguín, Pablo|||0000-0001-6068-7711
Ouharzoune, Allissa
Guillot, Régis
Lledós, Agustí|||0000-0001-7909-422X
Ujaque, Gregori|||0000-0001-5896-9998
Hannedouche, Jérôme
author Lepori, Clément
author_facet Lepori, Clément
Gómez-Orellana Seguín, Pablo|||0000-0001-6068-7711
Ouharzoune, Allissa
Guillot, Régis
Lledós, Agustí|||0000-0001-7909-422X
Ujaque, Gregori|||0000-0001-5896-9998
Hannedouche, Jérôme
author_role author
author2 Gómez-Orellana Seguín, Pablo|||0000-0001-6068-7711
Ouharzoune, Allissa
Guillot, Régis
Lledós, Agustí|||0000-0001-7909-422X
Ujaque, Gregori|||0000-0001-5896-9998
Hannedouche, Jérôme
author2_role author
author
author
author
author
author
dc.subject.none.fl_str_mv DFT calculations
Alkenes
Cobalt
Hydroamination
Mechanistic studies
Primary amines
topic DFT calculations
Alkenes
Cobalt
Hydroamination
Mechanistic studies
Primary amines
description A well-defined low-coordinate β-diketiminatocobalt(II) alkyl complex is reported as an active precatalyst for the selective alkene cyclohydroamination of unprotected primary amines under mild conditions (rt-90 °C). The reaction mechanism has been investigated by deuterium-labeling, kinetics, and stoichiometric experiments and in-depth computational DFT studies. On the basis of these studies, we propose a stepwise noninsertive mechanism that features a rate-determining nucleophilic attack of the amido group of a monomeric cobalt(II) amidoalkene-aminoalkene adduct intermediate to the noncoordinated pendant alkene followed by a rapid proton transfer from the coordinated aminoalkene to the cyclized adduct.
publishDate 2018
dc.date.none.fl_str_mv 2
2018-01-01
2018
2018-01-01
dc.type.none.fl_str_mv Article
http://purl.org/coar/resource_type/c_6501
AM
http://purl.org/coar/version/c_ab4af688f83e57aa
dc.type.openaire.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv https://ddd.uab.cat/record/279261
https://dx.doi.org/urn:doi:10.1021/acscatal.8b00631
url https://ddd.uab.cat/record/279261
https://dx.doi.org/urn:doi:10.1021/acscatal.8b00631
dc.language.none.fl_str_mv Inglés
eng
language_invalid_str_mv Inglés
language eng
dc.relation.none.fl_str_mv Agencia Estatal de Investigación https://doi.org/10.13039/501100011033 CTQ2017-87889-P
Ministerio de Economía y Competitividad https://doi.org/10.13039/501100003329 CTQ2016-81797-REDC
dc.rights.none.fl_str_mv open access
http://purl.org/coar/access_right/c_abf2
https://rightsstatements.org/vocab/InC/1.0/
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
https://rightsstatements.org/vocab/InC/1.0/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.source.none.fl_str_mv reponame:Dipòsit Digital de Documents de la UAB
instname:Universitat Autònoma de Barcelona
instname_str Universitat Autònoma de Barcelona
reponame_str Dipòsit Digital de Documents de la UAB
collection Dipòsit Digital de Documents de la UAB
repository.name.fl_str_mv
repository.mail.fl_str_mv
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