Dynamic multiligand catalysis: a polar to radical crossover strategy expands alkyne carboboration to unactivated secondary alkyl halides

We describe a dual strategy in Cu catalysis based on an unprecedented dynamic multiligand coordination pool that triggers cooperative polar/radical pathways in a single catalytic cycle. This strategy has been applied to address a restricting limitation inherent to Cu-catalyzed B2pin2-carboboration o...

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Autores: Kim-Lee, Shin Ho, Mauleón Pérez, Pablo, Gómez Arrayas, Ramón Jesús, Carretero Gonzálvez, Juan Carlos
Tipo de recurso: artículo
Fecha de publicación:2021
País:España
Institución:Universidad Autónoma de Madrid
Repositorio:Biblos-e Archivo. Repositorio Institucional de la UAM
Idioma:inglés
OAI Identifier:oai:repositorio.uam.es:10486/699380
Acceso en línea:http://hdl.handle.net/10486/699380
https://dx.doi.org/10.1016/j.chempr.2021.06.002
Access Level:acceso abierto
Palabra clave:Cu catalysis
Alkenyl boronates
Alkynes
Carboboration
Dynamic multiligand catalysis
Polar/radical crossover
Secondary alkyl halides
Tetrasubstituted alkenes
Química
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spelling Dynamic multiligand catalysis: a polar to radical crossover strategy expands alkyne carboboration to unactivated secondary alkyl halidesKim-Lee, Shin HoMauleón Pérez, PabloGómez Arrayas, Ramón JesúsCarretero Gonzálvez, Juan CarlosCu catalysisAlkenyl boronatesAlkynesCarboborationDynamic multiligand catalysisPolar/radical crossoverSecondary alkyl halidesTetrasubstituted alkenesQuímicaWe describe a dual strategy in Cu catalysis based on an unprecedented dynamic multiligand coordination pool that triggers cooperative polar/radical pathways in a single catalytic cycle. This strategy has been applied to address a restricting limitation inherent to Cu-catalyzed B2pin2-carboboration of alkynes—the very low reactivity of the intermediate vinyl-Cu(I) species, which renders conventional methods ineffective with alkyl electrophiles other than simple primary halides. The crossover strategy enabled by ligand exchange in an organometallic intermediate overcomes this reactivity issue, expanding the scope of carboboration to unactivated secondary alkyl halides, and opens new avenues to access stereodefined tetrasubstituted vinylboronates. The method is regio- and stereoselective, shows excellent functional group tolerance, and allows the incorporation of complex carbo- and heterocyclic fragments at either reaction partnerWe thank the Ministerio de Ciencia e Innovación (MICINN) and Fondo Europeo de Desarrollo Regional (FEDER, UE) for financial support (Agencia Estatal de Investigación/Project PGC2018-098660-B-I00)Cell PressDepartamento de Química OrgánicaFacultad de Ciencias20212021-06-29research articlehttp://purl.org/coar/resource_type/c_2df8fbb1AMhttp://purl.org/coar/version/c_ab4af688f83e57aainfo:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10486/699380https://dx.doi.org/10.1016/j.chempr.2021.06.002reponame:Biblos-e Archivo. Repositorio Institucional de la UAMinstname:Universidad Autónoma de MadridInglésengopen accesshttp://purl.org/coar/access_right/c_abf2info:eu-repo/semantics/openAccessoai:repositorio.uam.es:10486/6993802026-06-23T12:46:27Z
dc.title.none.fl_str_mv Dynamic multiligand catalysis: a polar to radical crossover strategy expands alkyne carboboration to unactivated secondary alkyl halides
title Dynamic multiligand catalysis: a polar to radical crossover strategy expands alkyne carboboration to unactivated secondary alkyl halides
spellingShingle Dynamic multiligand catalysis: a polar to radical crossover strategy expands alkyne carboboration to unactivated secondary alkyl halides
Kim-Lee, Shin Ho
Cu catalysis
Alkenyl boronates
Alkynes
Carboboration
Dynamic multiligand catalysis
Polar/radical crossover
Secondary alkyl halides
Tetrasubstituted alkenes
Química
title_short Dynamic multiligand catalysis: a polar to radical crossover strategy expands alkyne carboboration to unactivated secondary alkyl halides
title_full Dynamic multiligand catalysis: a polar to radical crossover strategy expands alkyne carboboration to unactivated secondary alkyl halides
title_fullStr Dynamic multiligand catalysis: a polar to radical crossover strategy expands alkyne carboboration to unactivated secondary alkyl halides
title_full_unstemmed Dynamic multiligand catalysis: a polar to radical crossover strategy expands alkyne carboboration to unactivated secondary alkyl halides
title_sort Dynamic multiligand catalysis: a polar to radical crossover strategy expands alkyne carboboration to unactivated secondary alkyl halides
dc.creator.none.fl_str_mv Kim-Lee, Shin Ho
Mauleón Pérez, Pablo
Gómez Arrayas, Ramón Jesús
Carretero Gonzálvez, Juan Carlos
author Kim-Lee, Shin Ho
author_facet Kim-Lee, Shin Ho
Mauleón Pérez, Pablo
Gómez Arrayas, Ramón Jesús
Carretero Gonzálvez, Juan Carlos
author_role author
author2 Mauleón Pérez, Pablo
Gómez Arrayas, Ramón Jesús
Carretero Gonzálvez, Juan Carlos
author2_role author
author
author
dc.contributor.none.fl_str_mv Departamento de Química Orgánica
Facultad de Ciencias
dc.subject.none.fl_str_mv Cu catalysis
Alkenyl boronates
Alkynes
Carboboration
Dynamic multiligand catalysis
Polar/radical crossover
Secondary alkyl halides
Tetrasubstituted alkenes
Química
topic Cu catalysis
Alkenyl boronates
Alkynes
Carboboration
Dynamic multiligand catalysis
Polar/radical crossover
Secondary alkyl halides
Tetrasubstituted alkenes
Química
description We describe a dual strategy in Cu catalysis based on an unprecedented dynamic multiligand coordination pool that triggers cooperative polar/radical pathways in a single catalytic cycle. This strategy has been applied to address a restricting limitation inherent to Cu-catalyzed B2pin2-carboboration of alkynes—the very low reactivity of the intermediate vinyl-Cu(I) species, which renders conventional methods ineffective with alkyl electrophiles other than simple primary halides. The crossover strategy enabled by ligand exchange in an organometallic intermediate overcomes this reactivity issue, expanding the scope of carboboration to unactivated secondary alkyl halides, and opens new avenues to access stereodefined tetrasubstituted vinylboronates. The method is regio- and stereoselective, shows excellent functional group tolerance, and allows the incorporation of complex carbo- and heterocyclic fragments at either reaction partner
publishDate 2021
dc.date.none.fl_str_mv 2021
2021-06-29
dc.type.none.fl_str_mv research article
http://purl.org/coar/resource_type/c_2df8fbb1
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 http://hdl.handle.net/10486/699380
https://dx.doi.org/10.1016/j.chempr.2021.06.002
url http://hdl.handle.net/10486/699380
https://dx.doi.org/10.1016/j.chempr.2021.06.002
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
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
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv Cell Press
publisher.none.fl_str_mv Cell Press
dc.source.none.fl_str_mv reponame:Biblos-e Archivo. Repositorio Institucional de la UAM
instname:Universidad Autónoma de Madrid
instname_str Universidad Autónoma de Madrid
reponame_str Biblos-e Archivo. Repositorio Institucional de la UAM
collection Biblos-e Archivo. Repositorio Institucional de la UAM
repository.name.fl_str_mv
repository.mail.fl_str_mv
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