Palladium-Catalyzed Enantioselective Arylation of Aryl Sulfenate Anions: A Combined Experimental and Computational Study

Autores
Jia, Tiezheng; Zhang, Mengnan; McCollom, Samuel P.; Bellomo Peraza, Ana Ines; Montel, Sonia; Mao, Jianyou; Dreher, Spencer D.; Welch, Christopher J.; Regalado, Erik L.; Williamson, R. Thomas; Manor, Brian C.; Tomson, Neil C.; Walsh, Patrick J.
Año de publicación
2017
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
A novel approach to produce chiral diaryl sulfoxides from aryl benzyl sulfoxides and aryl bromides via an enantioselective arylation of aryl sulfenate anions is reported. A (JosiPhos)Pd-based catalyst successfully promotes the asymmetric arylation reaction with good functional group compatibility. A wide range of enantioenriched diaryl, aryl heteroaryl, and even diheteroaryl sulfoxides were generated. Many of the sulfoxides prepared herein would be difficult to prepare via classic enantioselective oxidation of sulfides, including Ph(Ph-d5)SO (90% ee, 95% yield). A DFT-based computational study suggested that chiral induction originates from two primary factors: (i) both a kinetic and a thermodynamic preference for oxidative addition that places the bromide trans to the JosiPhos-diarylphosphine moiety and (ii) Curtin-Hammett-type control over the interconversion between O- and S-bound isomers of palladium sulfenate species following rapid interconversion between re- and si-bound transmetalation products, re/si-Pd-OSPh (re/si-PdO-trans).
Fil: Jia, Tiezheng. University of Pennsylvania; Estados Unidos
Fil: Zhang, Mengnan. University of Pennsylvania; Estados Unidos
Fil: McCollom, Samuel P.. University of Pennsylvania; Estados Unidos
Fil: Bellomo Peraza, Ana Ines. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Parque Centenario. Centro de Investigaciones en Bionanociencias ; Argentina
Fil: Montel, Sonia. University of Pennsylvania; Estados Unidos
Fil: Mao, Jianyou. Nanjing Tech University; República de China
Fil: Dreher, Spencer D.. Merck & Company; Estados Unidos
Fil: Welch, Christopher J.. Merck & Company; Estados Unidos
Fil: Regalado, Erik L.. Merck & Company; Estados Unidos
Fil: Williamson, R. Thomas. Merck & Company; Estados Unidos
Fil: Manor, Brian C.. Merck & Company; Estados Unidos
Fil: Tomson, Neil C.. University of Pennsylvania; Estados Unidos
Fil: Walsh, Patrick J.. University of Pennsylvania; Estados Unidos
Materia
Sulfoxide
Enantioselective
Josiphos
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:11336/51595
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/51595
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Palladium-Catalyzed Enantioselective Arylation of Aryl Sulfenate Anions: A Combined Experimental and Computational StudyJia, TiezhengZhang, MengnanMcCollom, Samuel P.Bellomo Peraza, Ana InesMontel, SoniaMao, JianyouDreher, Spencer D.Welch, Christopher J.Regalado, Erik L.Williamson, R. ThomasManor, Brian C.Tomson, Neil C.Walsh, Patrick J.SulfoxideEnantioselectiveJosiphoshttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1A novel approach to produce chiral diaryl sulfoxides from aryl benzyl sulfoxides and aryl bromides via an enantioselective arylation of aryl sulfenate anions is reported. A (JosiPhos)Pd-based catalyst successfully promotes the asymmetric arylation reaction with good functional group compatibility. A wide range of enantioenriched diaryl, aryl heteroaryl, and even diheteroaryl sulfoxides were generated. Many of the sulfoxides prepared herein would be difficult to prepare via classic enantioselective oxidation of sulfides, including Ph(Ph-d5)SO (90% ee, 95% yield). A DFT-based computational study suggested that chiral induction originates from two primary factors: (i) both a kinetic and a thermodynamic preference for oxidative addition that places the bromide trans to the JosiPhos-diarylphosphine moiety and (ii) Curtin-Hammett-type control over the interconversion between O- and S-bound isomers of palladium sulfenate species following rapid interconversion between re- and si-bound transmetalation products, re/si-Pd-OSPh (re/si-PdO-trans).Fil: Jia, Tiezheng. University of Pennsylvania; Estados UnidosFil: Zhang, Mengnan. University of Pennsylvania; Estados UnidosFil: McCollom, Samuel P.. University of Pennsylvania; Estados UnidosFil: Bellomo Peraza, Ana Ines. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Parque Centenario. Centro de Investigaciones en Bionanociencias ; ArgentinaFil: Montel, Sonia. University of Pennsylvania; Estados UnidosFil: Mao, Jianyou. Nanjing Tech University; República de ChinaFil: Dreher, Spencer D.. Merck & Company; Estados UnidosFil: Welch, Christopher J.. Merck & Company; Estados UnidosFil: Regalado, Erik L.. Merck & Company; Estados UnidosFil: Williamson, R. Thomas. Merck & Company; Estados UnidosFil: Manor, Brian C.. Merck & Company; Estados UnidosFil: Tomson, Neil C.. University of Pennsylvania; Estados UnidosFil: Walsh, Patrick J.. University of Pennsylvania; Estados UnidosAmerican Chemical Society2017-06info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/51595Jia, Tiezheng; Zhang, Mengnan; McCollom, Samuel P.; Bellomo Peraza, Ana Ines; Montel, Sonia; et al.; Palladium-Catalyzed Enantioselective Arylation of Aryl Sulfenate Anions: A Combined Experimental and Computational Study; American Chemical Society; Journal of the American Chemical Society; 139; 24; 6-2017; 8337-83450002-78631520-5126CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/jacs.7b03623info:eu-repo/semantics/altIdentifier/doi/10.1021/jacs.7b03623info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-22T11:15:24Zoai:ri.conicet.gov.ar:11336/51595instacron: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:34982025-10-22 11:15:25.195CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Palladium-Catalyzed Enantioselective Arylation of Aryl Sulfenate Anions: A Combined Experimental and Computational Study
title Palladium-Catalyzed Enantioselective Arylation of Aryl Sulfenate Anions: A Combined Experimental and Computational Study
spellingShingle Palladium-Catalyzed Enantioselective Arylation of Aryl Sulfenate Anions: A Combined Experimental and Computational Study
Jia, Tiezheng
Sulfoxide
Enantioselective
Josiphos
title_short Palladium-Catalyzed Enantioselective Arylation of Aryl Sulfenate Anions: A Combined Experimental and Computational Study
title_full Palladium-Catalyzed Enantioselective Arylation of Aryl Sulfenate Anions: A Combined Experimental and Computational Study
title_fullStr Palladium-Catalyzed Enantioselective Arylation of Aryl Sulfenate Anions: A Combined Experimental and Computational Study
title_full_unstemmed Palladium-Catalyzed Enantioselective Arylation of Aryl Sulfenate Anions: A Combined Experimental and Computational Study
title_sort Palladium-Catalyzed Enantioselective Arylation of Aryl Sulfenate Anions: A Combined Experimental and Computational Study
dc.creator.none.fl_str_mv Jia, Tiezheng
Zhang, Mengnan
McCollom, Samuel P.
Bellomo Peraza, Ana Ines
Montel, Sonia
Mao, Jianyou
Dreher, Spencer D.
Welch, Christopher J.
Regalado, Erik L.
Williamson, R. Thomas
Manor, Brian C.
Tomson, Neil C.
Walsh, Patrick J.
author Jia, Tiezheng
author_facet Jia, Tiezheng
Zhang, Mengnan
McCollom, Samuel P.
Bellomo Peraza, Ana Ines
Montel, Sonia
Mao, Jianyou
Dreher, Spencer D.
Welch, Christopher J.
Regalado, Erik L.
Williamson, R. Thomas
Manor, Brian C.
Tomson, Neil C.
Walsh, Patrick J.
author_role author
author2 Zhang, Mengnan
McCollom, Samuel P.
Bellomo Peraza, Ana Ines
Montel, Sonia
Mao, Jianyou
Dreher, Spencer D.
Welch, Christopher J.
Regalado, Erik L.
Williamson, R. Thomas
Manor, Brian C.
Tomson, Neil C.
Walsh, Patrick J.
author2_role author
author
author
author
author
author
author
author
author
author
author
author
dc.subject.none.fl_str_mv Sulfoxide
Enantioselective
Josiphos
topic Sulfoxide
Enantioselective
Josiphos
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv A novel approach to produce chiral diaryl sulfoxides from aryl benzyl sulfoxides and aryl bromides via an enantioselective arylation of aryl sulfenate anions is reported. A (JosiPhos)Pd-based catalyst successfully promotes the asymmetric arylation reaction with good functional group compatibility. A wide range of enantioenriched diaryl, aryl heteroaryl, and even diheteroaryl sulfoxides were generated. Many of the sulfoxides prepared herein would be difficult to prepare via classic enantioselective oxidation of sulfides, including Ph(Ph-d5)SO (90% ee, 95% yield). A DFT-based computational study suggested that chiral induction originates from two primary factors: (i) both a kinetic and a thermodynamic preference for oxidative addition that places the bromide trans to the JosiPhos-diarylphosphine moiety and (ii) Curtin-Hammett-type control over the interconversion between O- and S-bound isomers of palladium sulfenate species following rapid interconversion between re- and si-bound transmetalation products, re/si-Pd-OSPh (re/si-PdO-trans).
Fil: Jia, Tiezheng. University of Pennsylvania; Estados Unidos
Fil: Zhang, Mengnan. University of Pennsylvania; Estados Unidos
Fil: McCollom, Samuel P.. University of Pennsylvania; Estados Unidos
Fil: Bellomo Peraza, Ana Ines. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Parque Centenario. Centro de Investigaciones en Bionanociencias ; Argentina
Fil: Montel, Sonia. University of Pennsylvania; Estados Unidos
Fil: Mao, Jianyou. Nanjing Tech University; República de China
Fil: Dreher, Spencer D.. Merck & Company; Estados Unidos
Fil: Welch, Christopher J.. Merck & Company; Estados Unidos
Fil: Regalado, Erik L.. Merck & Company; Estados Unidos
Fil: Williamson, R. Thomas. Merck & Company; Estados Unidos
Fil: Manor, Brian C.. Merck & Company; Estados Unidos
Fil: Tomson, Neil C.. University of Pennsylvania; Estados Unidos
Fil: Walsh, Patrick J.. University of Pennsylvania; Estados Unidos
description A novel approach to produce chiral diaryl sulfoxides from aryl benzyl sulfoxides and aryl bromides via an enantioselective arylation of aryl sulfenate anions is reported. A (JosiPhos)Pd-based catalyst successfully promotes the asymmetric arylation reaction with good functional group compatibility. A wide range of enantioenriched diaryl, aryl heteroaryl, and even diheteroaryl sulfoxides were generated. Many of the sulfoxides prepared herein would be difficult to prepare via classic enantioselective oxidation of sulfides, including Ph(Ph-d5)SO (90% ee, 95% yield). A DFT-based computational study suggested that chiral induction originates from two primary factors: (i) both a kinetic and a thermodynamic preference for oxidative addition that places the bromide trans to the JosiPhos-diarylphosphine moiety and (ii) Curtin-Hammett-type control over the interconversion between O- and S-bound isomers of palladium sulfenate species following rapid interconversion between re- and si-bound transmetalation products, re/si-Pd-OSPh (re/si-PdO-trans).
publishDate 2017
dc.date.none.fl_str_mv 2017-06
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/11336/51595
Jia, Tiezheng; Zhang, Mengnan; McCollom, Samuel P.; Bellomo Peraza, Ana Ines; Montel, Sonia; et al.; Palladium-Catalyzed Enantioselective Arylation of Aryl Sulfenate Anions: A Combined Experimental and Computational Study; American Chemical Society; Journal of the American Chemical Society; 139; 24; 6-2017; 8337-8345
0002-7863
1520-5126
CONICET Digital
CONICET
url http://hdl.handle.net/11336/51595
identifier_str_mv Jia, Tiezheng; Zhang, Mengnan; McCollom, Samuel P.; Bellomo Peraza, Ana Ines; Montel, Sonia; et al.; Palladium-Catalyzed Enantioselective Arylation of Aryl Sulfenate Anions: A Combined Experimental and Computational Study; American Chemical Society; Journal of the American Chemical Society; 139; 24; 6-2017; 8337-8345
0002-7863
1520-5126
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/jacs.7b03623
info:eu-repo/semantics/altIdentifier/doi/10.1021/jacs.7b03623
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
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 12.982451

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