A wide mechanistic spectrum observed in three different reactions with organometallic reagents

Autores
Rodriguez, Cristian Ramon; Vazquez, Alvaro Joaquin; Sbarbati, Norma Ethel
Año de publicación
2010
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The halogen-lithium exchange reaction is of one of the most powerful method for the preparation of organolithium compounds, but its mechanism is still controversial. To afford some new elements, we synthesized a new suitable fast radical clock, bearing a phenyl group at the alkene C-terminal. The examination of some mechanistic clues, as well as the identification of the unexpected by-products allowed the conclusion that the reaction proceeds by a polar mechanism and no evidence for radicals were found. The second reaction discussed is the insertion of NO in the N-Li bond of lithium amides. Evidence for the involving of paramagnetic and nitrosonium intermediates, as well as equilibria between different reactive species were essential for the proposal of a whole complex mechanism, which was confirmed by theoretical calculations. Finally, results on the addition of heteroaromatic organocuprates to a,b-unsaturated substrates are presented. Several reaction conditions were looked for to lead the reaction toward the more interesting 1,4-conjugated addition. Thus, addition of up to 6 equivalents of TMSCl to the reaction with arylcuprates leads to a clean addition yielding more than 95% of the 1,4-addition product. A further objective of the paper is to show how the search of unexpected routes of reaction allowed developing original pathways to lead them toward the formation of appealing functionalized compounds. Copyright © 2010 John Wiley and Sons, Ltd.
Fil: Rodriguez, Cristian Ramon. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Orgánica; Argentina
Fil: Vazquez, Alvaro Joaquin. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Orgánica; Argentina
Fil: Sbarbati, Norma Ethel. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Orgánica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Materia
Halogen-Lithium Exchange
Heteroaromatic Organocuprates
No Insertion
Tmscl
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/67732
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/67732
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling A wide mechanistic spectrum observed in three different reactions with organometallic reagentsRodriguez, Cristian RamonVazquez, Alvaro JoaquinSbarbati, Norma EthelHalogen-Lithium ExchangeHeteroaromatic OrganocupratesNo InsertionTmsclhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The halogen-lithium exchange reaction is of one of the most powerful method for the preparation of organolithium compounds, but its mechanism is still controversial. To afford some new elements, we synthesized a new suitable fast radical clock, bearing a phenyl group at the alkene C-terminal. The examination of some mechanistic clues, as well as the identification of the unexpected by-products allowed the conclusion that the reaction proceeds by a polar mechanism and no evidence for radicals were found. The second reaction discussed is the insertion of NO in the N-Li bond of lithium amides. Evidence for the involving of paramagnetic and nitrosonium intermediates, as well as equilibria between different reactive species were essential for the proposal of a whole complex mechanism, which was confirmed by theoretical calculations. Finally, results on the addition of heteroaromatic organocuprates to a,b-unsaturated substrates are presented. Several reaction conditions were looked for to lead the reaction toward the more interesting 1,4-conjugated addition. Thus, addition of up to 6 equivalents of TMSCl to the reaction with arylcuprates leads to a clean addition yielding more than 95% of the 1,4-addition product. A further objective of the paper is to show how the search of unexpected routes of reaction allowed developing original pathways to lead them toward the formation of appealing functionalized compounds. Copyright © 2010 John Wiley and Sons, Ltd.Fil: Rodriguez, Cristian Ramon. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Orgánica; ArgentinaFil: Vazquez, Alvaro Joaquin. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Orgánica; ArgentinaFil: Sbarbati, Norma Ethel. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Orgánica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaJohn Wiley & Sons Ltd2010-10info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/67732Rodriguez, Cristian Ramon; Vazquez, Alvaro Joaquin; Sbarbati, Norma Ethel; A wide mechanistic spectrum observed in three different reactions with organometallic reagents; John Wiley & Sons Ltd; Journal Of Physical Organic Chemistry; 23; 10; 10-2010; 978-9840894-3230CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://onlinelibrary.wiley.com/doi/abs/10.1002/poc.1761info:eu-repo/semantics/altIdentifier/doi/10.1002/poc.1761info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:39:55Zoai:ri.conicet.gov.ar:11336/67732instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-09-29 10:39:55.524CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv A wide mechanistic spectrum observed in three different reactions with organometallic reagents
title A wide mechanistic spectrum observed in three different reactions with organometallic reagents
spellingShingle A wide mechanistic spectrum observed in three different reactions with organometallic reagents
Rodriguez, Cristian Ramon
Halogen-Lithium Exchange
Heteroaromatic Organocuprates
No Insertion
Tmscl
title_short A wide mechanistic spectrum observed in three different reactions with organometallic reagents
title_full A wide mechanistic spectrum observed in three different reactions with organometallic reagents
title_fullStr A wide mechanistic spectrum observed in three different reactions with organometallic reagents
title_full_unstemmed A wide mechanistic spectrum observed in three different reactions with organometallic reagents
title_sort A wide mechanistic spectrum observed in three different reactions with organometallic reagents
dc.creator.none.fl_str_mv Rodriguez, Cristian Ramon
Vazquez, Alvaro Joaquin
Sbarbati, Norma Ethel
author Rodriguez, Cristian Ramon
author_facet Rodriguez, Cristian Ramon
Vazquez, Alvaro Joaquin
Sbarbati, Norma Ethel
author_role author
author2 Vazquez, Alvaro Joaquin
Sbarbati, Norma Ethel
author2_role author
author
dc.subject.none.fl_str_mv Halogen-Lithium Exchange
Heteroaromatic Organocuprates
No Insertion
Tmscl
topic Halogen-Lithium Exchange
Heteroaromatic Organocuprates
No Insertion
Tmscl
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv The halogen-lithium exchange reaction is of one of the most powerful method for the preparation of organolithium compounds, but its mechanism is still controversial. To afford some new elements, we synthesized a new suitable fast radical clock, bearing a phenyl group at the alkene C-terminal. The examination of some mechanistic clues, as well as the identification of the unexpected by-products allowed the conclusion that the reaction proceeds by a polar mechanism and no evidence for radicals were found. The second reaction discussed is the insertion of NO in the N-Li bond of lithium amides. Evidence for the involving of paramagnetic and nitrosonium intermediates, as well as equilibria between different reactive species were essential for the proposal of a whole complex mechanism, which was confirmed by theoretical calculations. Finally, results on the addition of heteroaromatic organocuprates to a,b-unsaturated substrates are presented. Several reaction conditions were looked for to lead the reaction toward the more interesting 1,4-conjugated addition. Thus, addition of up to 6 equivalents of TMSCl to the reaction with arylcuprates leads to a clean addition yielding more than 95% of the 1,4-addition product. A further objective of the paper is to show how the search of unexpected routes of reaction allowed developing original pathways to lead them toward the formation of appealing functionalized compounds. Copyright © 2010 John Wiley and Sons, Ltd.
Fil: Rodriguez, Cristian Ramon. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Orgánica; Argentina
Fil: Vazquez, Alvaro Joaquin. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Orgánica; Argentina
Fil: Sbarbati, Norma Ethel. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Orgánica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
description The halogen-lithium exchange reaction is of one of the most powerful method for the preparation of organolithium compounds, but its mechanism is still controversial. To afford some new elements, we synthesized a new suitable fast radical clock, bearing a phenyl group at the alkene C-terminal. The examination of some mechanistic clues, as well as the identification of the unexpected by-products allowed the conclusion that the reaction proceeds by a polar mechanism and no evidence for radicals were found. The second reaction discussed is the insertion of NO in the N-Li bond of lithium amides. Evidence for the involving of paramagnetic and nitrosonium intermediates, as well as equilibria between different reactive species were essential for the proposal of a whole complex mechanism, which was confirmed by theoretical calculations. Finally, results on the addition of heteroaromatic organocuprates to a,b-unsaturated substrates are presented. Several reaction conditions were looked for to lead the reaction toward the more interesting 1,4-conjugated addition. Thus, addition of up to 6 equivalents of TMSCl to the reaction with arylcuprates leads to a clean addition yielding more than 95% of the 1,4-addition product. A further objective of the paper is to show how the search of unexpected routes of reaction allowed developing original pathways to lead them toward the formation of appealing functionalized compounds. Copyright © 2010 John Wiley and Sons, Ltd.
publishDate 2010
dc.date.none.fl_str_mv 2010-10
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/67732
Rodriguez, Cristian Ramon; Vazquez, Alvaro Joaquin; Sbarbati, Norma Ethel; A wide mechanistic spectrum observed in three different reactions with organometallic reagents; John Wiley & Sons Ltd; Journal Of Physical Organic Chemistry; 23; 10; 10-2010; 978-984
0894-3230
CONICET Digital
CONICET
url http://hdl.handle.net/11336/67732
identifier_str_mv Rodriguez, Cristian Ramon; Vazquez, Alvaro Joaquin; Sbarbati, Norma Ethel; A wide mechanistic spectrum observed in three different reactions with organometallic reagents; John Wiley & Sons Ltd; Journal Of Physical Organic Chemistry; 23; 10; 10-2010; 978-984
0894-3230
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/https://onlinelibrary.wiley.com/doi/abs/10.1002/poc.1761
info:eu-repo/semantics/altIdentifier/doi/10.1002/poc.1761
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
application/pdf
dc.publisher.none.fl_str_mv John Wiley & Sons Ltd
publisher.none.fl_str_mv John Wiley & Sons Ltd
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
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score 13.070432

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