Competitive reaction pathways for o-Anilide aryl radicals: 1,5-Or 1,6-hydrogen transfer versus nucleophilic coupling reactions. A novel rearrangement to afford an amidyl Radical

Autores
Rey, Valentina; Pierini, Adriana Beatriz; Peñeñory, Alicia Beatriz
Año de publicación
2009
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The photoinduced reactions of o-iodoanilides (o-IC6H 4N(Me)COR, 4a-d) with sulfur nucleophiles such as thiourea anion (1, -SCNH(NH2)), thioacetate anion (2, MeCOS-), and sulfide anion (3,S2-) follow different reaction channels, giving the sulfides by a radical nucleophilic substitution or the dehalogenated products by hydrogen atom transfer pathways. After an initial photoinduced electron transfer (PET) from 1 to iodide 4, the o-amide aryl radicals 12 are generated. These aryl radicals 12 afford alternative reaction pathways depending on the structure of the a-carbonyl moiety: (a) 12b (R = Me) adds to 1 to render the methylthio-substituted compounds by quenching the thiolate anion intermediate with MeI after irradiation; (b) 12c (R =-CH2Ph) follows a 1,5-hydrogen transfer to give a stabilized a-carbonyl radical (17); and (c) 12d (R = t-Bu) affords 1,6-hydrogen transfer, followed by a 1,4-aryl migration to render an amidyl radical (20), which is reduced to the N-benzyl-N,2- dimethylpropanamide (10). Together with this last rearranged product, the ipso substitution derivative was also observed. Similar results were obtained in the PET reactions of 4d (R = t-Bu) with anions 2 and 3 under entrainment conditions with the enolate anion from cyclohexenone (5) or thetert-butoxide anion (6). From this novel rearrangement, and only under reductive conditions by PET reaction with anion 5, iodide 4d (R = t-Bu) affords quantitatively the propanamide 10. The energetic of the intramolecular rearrangements followed by radicals 12b-d were rationalized by B3LYP/6-31+G* calculations.
Fil: Rey, Valentina. 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: Pierini, Adriana 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: 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
Materia
Radicals
Rearrangement
Sulfur Nucleophiles
Dft
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:11336/114344
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/114344
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Competitive reaction pathways for o-Anilide aryl radicals: 1,5-Or 1,6-hydrogen transfer versus nucleophilic coupling reactions. A novel rearrangement to afford an amidyl RadicalRey, ValentinaPierini, Adriana BeatrizPeñeñory, Alicia BeatrizRadicalsRearrangementSulfur NucleophilesDfthttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The photoinduced reactions of o-iodoanilides (o-IC6H 4N(Me)COR, 4a-d) with sulfur nucleophiles such as thiourea anion (1, -SCNH(NH2)), thioacetate anion (2, MeCOS-), and sulfide anion (3,S2-) follow different reaction channels, giving the sulfides by a radical nucleophilic substitution or the dehalogenated products by hydrogen atom transfer pathways. After an initial photoinduced electron transfer (PET) from 1 to iodide 4, the o-amide aryl radicals 12 are generated. These aryl radicals 12 afford alternative reaction pathways depending on the structure of the a-carbonyl moiety: (a) 12b (R = Me) adds to 1 to render the methylthio-substituted compounds by quenching the thiolate anion intermediate with MeI after irradiation; (b) 12c (R =-CH2Ph) follows a 1,5-hydrogen transfer to give a stabilized a-carbonyl radical (17); and (c) 12d (R = t-Bu) affords 1,6-hydrogen transfer, followed by a 1,4-aryl migration to render an amidyl radical (20), which is reduced to the N-benzyl-N,2- dimethylpropanamide (10). Together with this last rearranged product, the ipso substitution derivative was also observed. Similar results were obtained in the PET reactions of 4d (R = t-Bu) with anions 2 and 3 under entrainment conditions with the enolate anion from cyclohexenone (5) or thetert-butoxide anion (6). From this novel rearrangement, and only under reductive conditions by PET reaction with anion 5, iodide 4d (R = t-Bu) affords quantitatively the propanamide 10. The energetic of the intramolecular rearrangements followed by radicals 12b-d were rationalized by B3LYP/6-31+G* calculations.Fil: Rey, Valentina. 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: Pierini, Adriana 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: 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; ArgentinaAmerican Chemical Society2009-02info: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/11336/114344Rey, Valentina; Pierini, Adriana Beatriz; Peñeñory, Alicia Beatriz; Competitive reaction pathways for o-Anilide aryl radicals: 1,5-Or 1,6-hydrogen transfer versus nucleophilic coupling reactions. A novel rearrangement to afford an amidyl Radical; American Chemical Society; Journal of Organic Chemistry; 74; 3; 2-2009; 1223-12300022-32631520-6904CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/jo801892cinfo:eu-repo/semantics/altIdentifier/doi/10.1021/jo801892cinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-15T14:25:54Zoai:ri.conicet.gov.ar:11336/114344instacron: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 14:25:54.571CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Competitive reaction pathways for o-Anilide aryl radicals: 1,5-Or 1,6-hydrogen transfer versus nucleophilic coupling reactions. A novel rearrangement to afford an amidyl Radical
title Competitive reaction pathways for o-Anilide aryl radicals: 1,5-Or 1,6-hydrogen transfer versus nucleophilic coupling reactions. A novel rearrangement to afford an amidyl Radical
spellingShingle Competitive reaction pathways for o-Anilide aryl radicals: 1,5-Or 1,6-hydrogen transfer versus nucleophilic coupling reactions. A novel rearrangement to afford an amidyl Radical
Rey, Valentina
Radicals
Rearrangement
Sulfur Nucleophiles
Dft
title_short Competitive reaction pathways for o-Anilide aryl radicals: 1,5-Or 1,6-hydrogen transfer versus nucleophilic coupling reactions. A novel rearrangement to afford an amidyl Radical
title_full Competitive reaction pathways for o-Anilide aryl radicals: 1,5-Or 1,6-hydrogen transfer versus nucleophilic coupling reactions. A novel rearrangement to afford an amidyl Radical
title_fullStr Competitive reaction pathways for o-Anilide aryl radicals: 1,5-Or 1,6-hydrogen transfer versus nucleophilic coupling reactions. A novel rearrangement to afford an amidyl Radical
title_full_unstemmed Competitive reaction pathways for o-Anilide aryl radicals: 1,5-Or 1,6-hydrogen transfer versus nucleophilic coupling reactions. A novel rearrangement to afford an amidyl Radical
title_sort Competitive reaction pathways for o-Anilide aryl radicals: 1,5-Or 1,6-hydrogen transfer versus nucleophilic coupling reactions. A novel rearrangement to afford an amidyl Radical
dc.creator.none.fl_str_mv Rey, Valentina
Pierini, Adriana Beatriz
Peñeñory, Alicia Beatriz
author Rey, Valentina
author_facet Rey, Valentina
Pierini, Adriana Beatriz
Peñeñory, Alicia Beatriz
author_role author
author2 Pierini, Adriana Beatriz
Peñeñory, Alicia Beatriz
author2_role author
author
dc.subject.none.fl_str_mv Radicals
Rearrangement
Sulfur Nucleophiles
Dft
topic Radicals
Rearrangement
Sulfur Nucleophiles
Dft
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 photoinduced reactions of o-iodoanilides (o-IC6H 4N(Me)COR, 4a-d) with sulfur nucleophiles such as thiourea anion (1, -SCNH(NH2)), thioacetate anion (2, MeCOS-), and sulfide anion (3,S2-) follow different reaction channels, giving the sulfides by a radical nucleophilic substitution or the dehalogenated products by hydrogen atom transfer pathways. After an initial photoinduced electron transfer (PET) from 1 to iodide 4, the o-amide aryl radicals 12 are generated. These aryl radicals 12 afford alternative reaction pathways depending on the structure of the a-carbonyl moiety: (a) 12b (R = Me) adds to 1 to render the methylthio-substituted compounds by quenching the thiolate anion intermediate with MeI after irradiation; (b) 12c (R =-CH2Ph) follows a 1,5-hydrogen transfer to give a stabilized a-carbonyl radical (17); and (c) 12d (R = t-Bu) affords 1,6-hydrogen transfer, followed by a 1,4-aryl migration to render an amidyl radical (20), which is reduced to the N-benzyl-N,2- dimethylpropanamide (10). Together with this last rearranged product, the ipso substitution derivative was also observed. Similar results were obtained in the PET reactions of 4d (R = t-Bu) with anions 2 and 3 under entrainment conditions with the enolate anion from cyclohexenone (5) or thetert-butoxide anion (6). From this novel rearrangement, and only under reductive conditions by PET reaction with anion 5, iodide 4d (R = t-Bu) affords quantitatively the propanamide 10. The energetic of the intramolecular rearrangements followed by radicals 12b-d were rationalized by B3LYP/6-31+G* calculations.
Fil: Rey, Valentina. 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: Pierini, Adriana 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: 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
description The photoinduced reactions of o-iodoanilides (o-IC6H 4N(Me)COR, 4a-d) with sulfur nucleophiles such as thiourea anion (1, -SCNH(NH2)), thioacetate anion (2, MeCOS-), and sulfide anion (3,S2-) follow different reaction channels, giving the sulfides by a radical nucleophilic substitution or the dehalogenated products by hydrogen atom transfer pathways. After an initial photoinduced electron transfer (PET) from 1 to iodide 4, the o-amide aryl radicals 12 are generated. These aryl radicals 12 afford alternative reaction pathways depending on the structure of the a-carbonyl moiety: (a) 12b (R = Me) adds to 1 to render the methylthio-substituted compounds by quenching the thiolate anion intermediate with MeI after irradiation; (b) 12c (R =-CH2Ph) follows a 1,5-hydrogen transfer to give a stabilized a-carbonyl radical (17); and (c) 12d (R = t-Bu) affords 1,6-hydrogen transfer, followed by a 1,4-aryl migration to render an amidyl radical (20), which is reduced to the N-benzyl-N,2- dimethylpropanamide (10). Together with this last rearranged product, the ipso substitution derivative was also observed. Similar results were obtained in the PET reactions of 4d (R = t-Bu) with anions 2 and 3 under entrainment conditions with the enolate anion from cyclohexenone (5) or thetert-butoxide anion (6). From this novel rearrangement, and only under reductive conditions by PET reaction with anion 5, iodide 4d (R = t-Bu) affords quantitatively the propanamide 10. The energetic of the intramolecular rearrangements followed by radicals 12b-d were rationalized by B3LYP/6-31+G* calculations.
publishDate 2009
dc.date.none.fl_str_mv 2009-02
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/11336/114344
Rey, Valentina; Pierini, Adriana Beatriz; Peñeñory, Alicia Beatriz; Competitive reaction pathways for o-Anilide aryl radicals: 1,5-Or 1,6-hydrogen transfer versus nucleophilic coupling reactions. A novel rearrangement to afford an amidyl Radical; American Chemical Society; Journal of Organic Chemistry; 74; 3; 2-2009; 1223-1230
0022-3263
1520-6904
CONICET Digital
CONICET
url http://hdl.handle.net/11336/114344
identifier_str_mv Rey, Valentina; Pierini, Adriana Beatriz; Peñeñory, Alicia Beatriz; Competitive reaction pathways for o-Anilide aryl radicals: 1,5-Or 1,6-hydrogen transfer versus nucleophilic coupling reactions. A novel rearrangement to afford an amidyl Radical; American Chemical Society; Journal of Organic Chemistry; 74; 3; 2-2009; 1223-1230
0022-3263
1520-6904
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://pubs.acs.org/doi/10.1021/jo801892c
info:eu-repo/semantics/altIdentifier/doi/10.1021/jo801892c
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 American Chemical Society
publisher.none.fl_str_mv American Chemical Society
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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