Breaking bonds with electrons: stepwise and concerted reductive cleavage of C–S, C–Se and Se–CN bonds in phenacylthiocyanates and phenacylselenocyanates

Autores
Bouchet, Lydia María; Peñeñory, Alicia Beatriz; Robert, Marc; Argüello, Juan Elias
Año de publicación
2015
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The mechanistic aspects of the electrochemical reduction of phenacylthio- and selenocyanates have been studied. With phenacylthiocyanates (1), a change in the reductive cleavage mechanism is observed as a function of the substituent on the phenyl ring. While a stepwise mechanism involving the intermediacy of a radical anion is followed for substrates bearing a strong electron withdrawing group, such as cyano and nitro substituent (1d, 1e), and a concerted mechanism is favoured for compounds bearing an electron-donating or no substituent on the phenyl ring (1a–c). A regioselective bond cleavage leads to the fragmentation of the CH2–S bond with all compounds 1a–e, further yielding the corresponding 1,4-diketone (3) as products. Contrastingly, with phenacylselenocyanates (2), two different reductive cleavages occur involving the breaking of both the CH2–Se and Se–CN bonds. Several products are obtained, all coming from nucleophilic attack at the α (phenacyl) carbon or the selenium atom.
Fil: Bouchet, Lydia María. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Peñeñory, Alicia Beatriz. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Robert, Marc. Université Paris Diderot - Paris 7; Francia
Fil: Argüello, Juan Elias. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Materia
REDUCTION
ELECTROCHEMISTRY
SULPHIDES
SELENIDES
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:11336/43397
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/43397
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Breaking bonds with electrons: stepwise and concerted reductive cleavage of C–S, C–Se and Se–CN bonds in phenacylthiocyanates and phenacylselenocyanatesBouchet, Lydia MaríaPeñeñory, Alicia BeatrizRobert, MarcArgüello, Juan EliasREDUCTIONELECTROCHEMISTRYSULPHIDESSELENIDEShttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The mechanistic aspects of the electrochemical reduction of phenacylthio- and selenocyanates have been studied. With phenacylthiocyanates (1), a change in the reductive cleavage mechanism is observed as a function of the substituent on the phenyl ring. While a stepwise mechanism involving the intermediacy of a radical anion is followed for substrates bearing a strong electron withdrawing group, such as cyano and nitro substituent (1d, 1e), and a concerted mechanism is favoured for compounds bearing an electron-donating or no substituent on the phenyl ring (1a–c). A regioselective bond cleavage leads to the fragmentation of the CH2–S bond with all compounds 1a–e, further yielding the corresponding 1,4-diketone (3) as products. Contrastingly, with phenacylselenocyanates (2), two different reductive cleavages occur involving the breaking of both the CH2–Se and Se–CN bonds. Several products are obtained, all coming from nucleophilic attack at the α (phenacyl) carbon or the selenium atom.Fil: Bouchet, Lydia María. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Peñeñory, Alicia Beatriz. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Robert, Marc. Université Paris Diderot - Paris 7; FranciaFil: Argüello, Juan Elias. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaRoyal Society of Chemistry2015-01info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/43397Bouchet, Lydia María; Peñeñory, Alicia Beatriz; Robert, Marc ; Argüello, Juan Elias; Breaking bonds with electrons: stepwise and concerted reductive cleavage of C–S, C–Se and Se–CN bonds in phenacylthiocyanates and phenacylselenocyanates; Royal Society of Chemistry; RSC Advances; 5; 16; 1-2015; 11753-117602046-2069CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1039/c4ra16154hinfo:eu-repo/semantics/altIdentifier/url/http://pubs.rsc.org/en/Content/ArticleLanding/2015/RA/C4RA16154Hinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-15T15:08:41Zoai:ri.conicet.gov.ar:11336/43397instacron: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:34982025-10-15 15:08:41.445CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Breaking bonds with electrons: stepwise and concerted reductive cleavage of C–S, C–Se and Se–CN bonds in phenacylthiocyanates and phenacylselenocyanates
title Breaking bonds with electrons: stepwise and concerted reductive cleavage of C–S, C–Se and Se–CN bonds in phenacylthiocyanates and phenacylselenocyanates
spellingShingle Breaking bonds with electrons: stepwise and concerted reductive cleavage of C–S, C–Se and Se–CN bonds in phenacylthiocyanates and phenacylselenocyanates
Bouchet, Lydia María
REDUCTION
ELECTROCHEMISTRY
SULPHIDES
SELENIDES
title_short Breaking bonds with electrons: stepwise and concerted reductive cleavage of C–S, C–Se and Se–CN bonds in phenacylthiocyanates and phenacylselenocyanates
title_full Breaking bonds with electrons: stepwise and concerted reductive cleavage of C–S, C–Se and Se–CN bonds in phenacylthiocyanates and phenacylselenocyanates
title_fullStr Breaking bonds with electrons: stepwise and concerted reductive cleavage of C–S, C–Se and Se–CN bonds in phenacylthiocyanates and phenacylselenocyanates
title_full_unstemmed Breaking bonds with electrons: stepwise and concerted reductive cleavage of C–S, C–Se and Se–CN bonds in phenacylthiocyanates and phenacylselenocyanates
title_sort Breaking bonds with electrons: stepwise and concerted reductive cleavage of C–S, C–Se and Se–CN bonds in phenacylthiocyanates and phenacylselenocyanates
dc.creator.none.fl_str_mv Bouchet, Lydia María
Peñeñory, Alicia Beatriz
Robert, Marc
Argüello, Juan Elias
author Bouchet, Lydia María
author_facet Bouchet, Lydia María
Peñeñory, Alicia Beatriz
Robert, Marc
Argüello, Juan Elias
author_role author
author2 Peñeñory, Alicia Beatriz
Robert, Marc
Argüello, Juan Elias
author2_role author
author
author
dc.subject.none.fl_str_mv REDUCTION
ELECTROCHEMISTRY
SULPHIDES
SELENIDES
topic REDUCTION
ELECTROCHEMISTRY
SULPHIDES
SELENIDES
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 mechanistic aspects of the electrochemical reduction of phenacylthio- and selenocyanates have been studied. With phenacylthiocyanates (1), a change in the reductive cleavage mechanism is observed as a function of the substituent on the phenyl ring. While a stepwise mechanism involving the intermediacy of a radical anion is followed for substrates bearing a strong electron withdrawing group, such as cyano and nitro substituent (1d, 1e), and a concerted mechanism is favoured for compounds bearing an electron-donating or no substituent on the phenyl ring (1a–c). A regioselective bond cleavage leads to the fragmentation of the CH2–S bond with all compounds 1a–e, further yielding the corresponding 1,4-diketone (3) as products. Contrastingly, with phenacylselenocyanates (2), two different reductive cleavages occur involving the breaking of both the CH2–Se and Se–CN bonds. Several products are obtained, all coming from nucleophilic attack at the α (phenacyl) carbon or the selenium atom.
Fil: Bouchet, Lydia María. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Peñeñory, Alicia Beatriz. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Robert, Marc. Université Paris Diderot - Paris 7; Francia
Fil: Argüello, Juan Elias. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
description The mechanistic aspects of the electrochemical reduction of phenacylthio- and selenocyanates have been studied. With phenacylthiocyanates (1), a change in the reductive cleavage mechanism is observed as a function of the substituent on the phenyl ring. While a stepwise mechanism involving the intermediacy of a radical anion is followed for substrates bearing a strong electron withdrawing group, such as cyano and nitro substituent (1d, 1e), and a concerted mechanism is favoured for compounds bearing an electron-donating or no substituent on the phenyl ring (1a–c). A regioselective bond cleavage leads to the fragmentation of the CH2–S bond with all compounds 1a–e, further yielding the corresponding 1,4-diketone (3) as products. Contrastingly, with phenacylselenocyanates (2), two different reductive cleavages occur involving the breaking of both the CH2–Se and Se–CN bonds. Several products are obtained, all coming from nucleophilic attack at the α (phenacyl) carbon or the selenium atom.
publishDate 2015
dc.date.none.fl_str_mv 2015-01
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/11336/43397
Bouchet, Lydia María; Peñeñory, Alicia Beatriz; Robert, Marc ; Argüello, Juan Elias; Breaking bonds with electrons: stepwise and concerted reductive cleavage of C–S, C–Se and Se–CN bonds in phenacylthiocyanates and phenacylselenocyanates; Royal Society of Chemistry; RSC Advances; 5; 16; 1-2015; 11753-11760
2046-2069
CONICET Digital
CONICET
url http://hdl.handle.net/11336/43397
identifier_str_mv Bouchet, Lydia María; Peñeñory, Alicia Beatriz; Robert, Marc ; Argüello, Juan Elias; Breaking bonds with electrons: stepwise and concerted reductive cleavage of C–S, C–Se and Se–CN bonds in phenacylthiocyanates and phenacylselenocyanates; Royal Society of Chemistry; RSC Advances; 5; 16; 1-2015; 11753-11760
2046-2069
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1039/c4ra16154h
info:eu-repo/semantics/altIdentifier/url/http://pubs.rsc.org/en/Content/ArticleLanding/2015/RA/C4RA16154H
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
application/pdf
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: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 13.22299

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