A Chiral Bis(arsine) Ligand: synthesis and applications in Palladium catalyzed asymmetric Allylic Alkylations

Autores
Uberman, Paula Marina; Caira, Mino R.; Martín, Sandra Elizabeth
Año de publicación
2013
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The new chiral bis(arsine) ligand N,N′-bis[2′- (diphenylarsino)benzoyl]-(1R,2R)-cyclohexanediamine (BiAsBA, 3), based on the backbone of the Trost modular ligand (TML), was synthesized in three steps. A useful approach to introduce the −AsPh2 group on arsine ligands by Pd-catalyzed arsination was used. The molecular structure and configuration of the BiAsBA ligand was determined by single-crystal X-ray crystallography. In the asymmetric allylic alkylation of 1,3-diphenyl-2- propenyl acetate with dimethyl malonate very high to complete conversion and modest enantioselectivity were achieved. Despite the low enantioselectivity obtained, the bis(arsine) ligand BiAsBA showed significant potential, since it provided a higher ee value than the phosphorus-containing homologous “Trost standard ligand” (TSL) with the same substrate.
Fil: Uberman, Paula Marina. 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: Caira, Mino R.. University of Cape Town; Sudáfrica
Fil: Martín, Sandra Elizabeth. 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
Arsine Chiral Ligand
Asymmetric Allylic Alkylation
Palladium
Catalyzed Arsination
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:11336/25413
Acceder
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network_acronym_str CONICETDig
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network_name_str CONICET Digital (CONICET)
spelling A Chiral Bis(arsine) Ligand: synthesis and applications in Palladium catalyzed asymmetric Allylic AlkylationsUberman, Paula MarinaCaira, Mino R.Martín, Sandra ElizabethArsine Chiral LigandAsymmetric Allylic AlkylationPalladiumCatalyzed Arsinationhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The new chiral bis(arsine) ligand N,N′-bis[2′- (diphenylarsino)benzoyl]-(1R,2R)-cyclohexanediamine (BiAsBA, 3), based on the backbone of the Trost modular ligand (TML), was synthesized in three steps. A useful approach to introduce the −AsPh2 group on arsine ligands by Pd-catalyzed arsination was used. The molecular structure and configuration of the BiAsBA ligand was determined by single-crystal X-ray crystallography. In the asymmetric allylic alkylation of 1,3-diphenyl-2- propenyl acetate with dimethyl malonate very high to complete conversion and modest enantioselectivity were achieved. Despite the low enantioselectivity obtained, the bis(arsine) ligand BiAsBA showed significant potential, since it provided a higher ee value than the phosphorus-containing homologous “Trost standard ligand” (TSL) with the same substrate.Fil: Uberman, Paula Marina. 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: Caira, Mino R.. University of Cape Town; SudáfricaFil: Martín, Sandra Elizabeth. 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 Society2013-05info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/25413Uberman, Paula Marina; Caira, Mino R.; Martín, Sandra Elizabeth; A Chiral Bis(arsine) Ligand: synthesis and applications in Palladium catalyzed asymmetric Allylic Alkylations; American Chemical Society; Organometallics; 32; 11; 5-2013; 3220-32260276-7333CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1021/om400144sinfo:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/om400144sinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T09:44:07Zoai:ri.conicet.gov.ar:11336/25413instacron: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:34982025-09-03 09:44:07.36CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv A Chiral Bis(arsine) Ligand: synthesis and applications in Palladium catalyzed asymmetric Allylic Alkylations
title A Chiral Bis(arsine) Ligand: synthesis and applications in Palladium catalyzed asymmetric Allylic Alkylations
spellingShingle A Chiral Bis(arsine) Ligand: synthesis and applications in Palladium catalyzed asymmetric Allylic Alkylations
Uberman, Paula Marina
Arsine Chiral Ligand
Asymmetric Allylic Alkylation
Palladium
Catalyzed Arsination
title_short A Chiral Bis(arsine) Ligand: synthesis and applications in Palladium catalyzed asymmetric Allylic Alkylations
title_full A Chiral Bis(arsine) Ligand: synthesis and applications in Palladium catalyzed asymmetric Allylic Alkylations
title_fullStr A Chiral Bis(arsine) Ligand: synthesis and applications in Palladium catalyzed asymmetric Allylic Alkylations
title_full_unstemmed A Chiral Bis(arsine) Ligand: synthesis and applications in Palladium catalyzed asymmetric Allylic Alkylations
title_sort A Chiral Bis(arsine) Ligand: synthesis and applications in Palladium catalyzed asymmetric Allylic Alkylations
dc.creator.none.fl_str_mv Uberman, Paula Marina
Caira, Mino R.
Martín, Sandra Elizabeth
author Uberman, Paula Marina
author_facet Uberman, Paula Marina
Caira, Mino R.
Martín, Sandra Elizabeth
author_role author
author2 Caira, Mino R.
Martín, Sandra Elizabeth
author2_role author
author
dc.subject.none.fl_str_mv Arsine Chiral Ligand
Asymmetric Allylic Alkylation
Palladium
Catalyzed Arsination
topic Arsine Chiral Ligand
Asymmetric Allylic Alkylation
Palladium
Catalyzed Arsination
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 new chiral bis(arsine) ligand N,N′-bis[2′- (diphenylarsino)benzoyl]-(1R,2R)-cyclohexanediamine (BiAsBA, 3), based on the backbone of the Trost modular ligand (TML), was synthesized in three steps. A useful approach to introduce the −AsPh2 group on arsine ligands by Pd-catalyzed arsination was used. The molecular structure and configuration of the BiAsBA ligand was determined by single-crystal X-ray crystallography. In the asymmetric allylic alkylation of 1,3-diphenyl-2- propenyl acetate with dimethyl malonate very high to complete conversion and modest enantioselectivity were achieved. Despite the low enantioselectivity obtained, the bis(arsine) ligand BiAsBA showed significant potential, since it provided a higher ee value than the phosphorus-containing homologous “Trost standard ligand” (TSL) with the same substrate.
Fil: Uberman, Paula Marina. 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: Caira, Mino R.. University of Cape Town; Sudáfrica
Fil: Martín, Sandra Elizabeth. 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 new chiral bis(arsine) ligand N,N′-bis[2′- (diphenylarsino)benzoyl]-(1R,2R)-cyclohexanediamine (BiAsBA, 3), based on the backbone of the Trost modular ligand (TML), was synthesized in three steps. A useful approach to introduce the −AsPh2 group on arsine ligands by Pd-catalyzed arsination was used. The molecular structure and configuration of the BiAsBA ligand was determined by single-crystal X-ray crystallography. In the asymmetric allylic alkylation of 1,3-diphenyl-2- propenyl acetate with dimethyl malonate very high to complete conversion and modest enantioselectivity were achieved. Despite the low enantioselectivity obtained, the bis(arsine) ligand BiAsBA showed significant potential, since it provided a higher ee value than the phosphorus-containing homologous “Trost standard ligand” (TSL) with the same substrate.
publishDate 2013
dc.date.none.fl_str_mv 2013-05
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/11336/25413
Uberman, Paula Marina; Caira, Mino R.; Martín, Sandra Elizabeth; A Chiral Bis(arsine) Ligand: synthesis and applications in Palladium catalyzed asymmetric Allylic Alkylations; American Chemical Society; Organometallics; 32; 11; 5-2013; 3220-3226
0276-7333
CONICET Digital
CONICET
url http://hdl.handle.net/11336/25413
identifier_str_mv Uberman, Paula Marina; Caira, Mino R.; Martín, Sandra Elizabeth; A Chiral Bis(arsine) Ligand: synthesis and applications in Palladium catalyzed asymmetric Allylic Alkylations; American Chemical Society; Organometallics; 32; 11; 5-2013; 3220-3226
0276-7333
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1021/om400144s
info:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/om400144s
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
_version_ 1842268646356811776
score 13.13397

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