Nickel-catalyzed allylic alkylation with diarylmethane pronucleophiles: Reaction development and mechanistic insights

Autores
Sha, Sheng Chun; Jiang, Hui; Mao, Jianyou; Bellomo Peraza, Ana Ines; Jeong, Soo A.; Walsh, Patrick J.
Año de publicación
2016
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Palladium-catalyzed allylic substitution reactions are among the most efficient methods to construct C-C bonds between sp3-hybridized carbon atoms. In contrast, much less work has been done with nickel catalysts, perhaps because of the different mechanisms of the allylic substitution reactions. Palladium catalysts generally undergo substitution by a "soft"-nucleophile pathway, wherein the nucleophile attacks the allyl group externally. Nickel catalysts are usually paired with "hard" nucleophiles, which attack the metal before C-C bond formation. Introduced herein is a rare nickel-based catalyst which promotes substitution with diarylmethane pronucleophiles by the soft-nucleophile pathway. Preliminary studies on the asymmetric allylic alkylation are promising. Just a softy: Contrary to what would be predicted, organosodium nucleophiles derived from diarylmethane pronucleophiles are shown to behave as soft nucleophiles in nickel-catalyzed allylic substitution reactions. This general reaction is demonstrated to proceed through a double inversion pathway. A promising asymmetric version is presented.
Fil: Sha, Sheng Chun. University of Pennsylvania; Estados Unidos
Fil: Jiang, Hui. University of Pennsylvania; Estados Unidos
Fil: Mao, Jianyou. 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 "Elizabeth Jares Erijman"; Argentina. University of Pennsylvania; Estados Unidos
Fil: Jeong, Soo A.. University of Pennsylvania; Estados Unidos
Fil: Walsh, Patrick J.. University of Pennsylvania; Estados Unidos
Materia
Allylic Compounds
Asymmetric Catalysis
Cross-Coupling
Nickel
Synthetic Methods
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:11336/51133
Acceder
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network_name_str CONICET Digital (CONICET)
spelling Nickel-catalyzed allylic alkylation with diarylmethane pronucleophiles: Reaction development and mechanistic insightsSha, Sheng ChunJiang, HuiMao, JianyouBellomo Peraza, Ana InesJeong, Soo A.Walsh, Patrick J.Allylic CompoundsAsymmetric CatalysisCross-CouplingNickelSynthetic Methodshttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Palladium-catalyzed allylic substitution reactions are among the most efficient methods to construct C-C bonds between sp3-hybridized carbon atoms. In contrast, much less work has been done with nickel catalysts, perhaps because of the different mechanisms of the allylic substitution reactions. Palladium catalysts generally undergo substitution by a "soft"-nucleophile pathway, wherein the nucleophile attacks the allyl group externally. Nickel catalysts are usually paired with "hard" nucleophiles, which attack the metal before C-C bond formation. Introduced herein is a rare nickel-based catalyst which promotes substitution with diarylmethane pronucleophiles by the soft-nucleophile pathway. Preliminary studies on the asymmetric allylic alkylation are promising. Just a softy: Contrary to what would be predicted, organosodium nucleophiles derived from diarylmethane pronucleophiles are shown to behave as soft nucleophiles in nickel-catalyzed allylic substitution reactions. This general reaction is demonstrated to proceed through a double inversion pathway. A promising asymmetric version is presented.Fil: Sha, Sheng Chun. University of Pennsylvania; Estados UnidosFil: Jiang, Hui. University of Pennsylvania; Estados UnidosFil: Mao, Jianyou. 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 "Elizabeth Jares Erijman"; Argentina. University of Pennsylvania; Estados UnidosFil: Jeong, Soo A.. University of Pennsylvania; Estados UnidosFil: Walsh, Patrick J.. University of Pennsylvania; Estados UnidosWiley VCH Verlag2016-01-03info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/51133Sha, Sheng Chun; Jiang, Hui; Mao, Jianyou; Bellomo Peraza, Ana Ines; Jeong, Soo A.; et al.; Nickel-catalyzed allylic alkylation with diarylmethane pronucleophiles: Reaction development and mechanistic insights; Wiley VCH Verlag; Angewandte Chemie; 55; 3; 3-1-2016; 1070-10741433-7851CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1002/anie.201507494info:eu-repo/semantics/altIdentifier/url/https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.201507494info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-15T14:44:14Zoai:ri.conicet.gov.ar:11336/51133instacron: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 14:44:15.294CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Nickel-catalyzed allylic alkylation with diarylmethane pronucleophiles: Reaction development and mechanistic insights
title Nickel-catalyzed allylic alkylation with diarylmethane pronucleophiles: Reaction development and mechanistic insights
spellingShingle Nickel-catalyzed allylic alkylation with diarylmethane pronucleophiles: Reaction development and mechanistic insights
Sha, Sheng Chun
Allylic Compounds
Asymmetric Catalysis
Cross-Coupling
Nickel
Synthetic Methods
title_short Nickel-catalyzed allylic alkylation with diarylmethane pronucleophiles: Reaction development and mechanistic insights
title_full Nickel-catalyzed allylic alkylation with diarylmethane pronucleophiles: Reaction development and mechanistic insights
title_fullStr Nickel-catalyzed allylic alkylation with diarylmethane pronucleophiles: Reaction development and mechanistic insights
title_full_unstemmed Nickel-catalyzed allylic alkylation with diarylmethane pronucleophiles: Reaction development and mechanistic insights
title_sort Nickel-catalyzed allylic alkylation with diarylmethane pronucleophiles: Reaction development and mechanistic insights
dc.creator.none.fl_str_mv Sha, Sheng Chun
Jiang, Hui
Mao, Jianyou
Bellomo Peraza, Ana Ines
Jeong, Soo A.
Walsh, Patrick J.
author Sha, Sheng Chun
author_facet Sha, Sheng Chun
Jiang, Hui
Mao, Jianyou
Bellomo Peraza, Ana Ines
Jeong, Soo A.
Walsh, Patrick J.
author_role author
author2 Jiang, Hui
Mao, Jianyou
Bellomo Peraza, Ana Ines
Jeong, Soo A.
Walsh, Patrick J.
author2_role author
author
author
author
author
dc.subject.none.fl_str_mv Allylic Compounds
Asymmetric Catalysis
Cross-Coupling
Nickel
Synthetic Methods
topic Allylic Compounds
Asymmetric Catalysis
Cross-Coupling
Nickel
Synthetic Methods
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Palladium-catalyzed allylic substitution reactions are among the most efficient methods to construct C-C bonds between sp3-hybridized carbon atoms. In contrast, much less work has been done with nickel catalysts, perhaps because of the different mechanisms of the allylic substitution reactions. Palladium catalysts generally undergo substitution by a "soft"-nucleophile pathway, wherein the nucleophile attacks the allyl group externally. Nickel catalysts are usually paired with "hard" nucleophiles, which attack the metal before C-C bond formation. Introduced herein is a rare nickel-based catalyst which promotes substitution with diarylmethane pronucleophiles by the soft-nucleophile pathway. Preliminary studies on the asymmetric allylic alkylation are promising. Just a softy: Contrary to what would be predicted, organosodium nucleophiles derived from diarylmethane pronucleophiles are shown to behave as soft nucleophiles in nickel-catalyzed allylic substitution reactions. This general reaction is demonstrated to proceed through a double inversion pathway. A promising asymmetric version is presented.
Fil: Sha, Sheng Chun. University of Pennsylvania; Estados Unidos
Fil: Jiang, Hui. University of Pennsylvania; Estados Unidos
Fil: Mao, Jianyou. 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 "Elizabeth Jares Erijman"; Argentina. University of Pennsylvania; Estados Unidos
Fil: Jeong, Soo A.. University of Pennsylvania; Estados Unidos
Fil: Walsh, Patrick J.. University of Pennsylvania; Estados Unidos
description Palladium-catalyzed allylic substitution reactions are among the most efficient methods to construct C-C bonds between sp3-hybridized carbon atoms. In contrast, much less work has been done with nickel catalysts, perhaps because of the different mechanisms of the allylic substitution reactions. Palladium catalysts generally undergo substitution by a "soft"-nucleophile pathway, wherein the nucleophile attacks the allyl group externally. Nickel catalysts are usually paired with "hard" nucleophiles, which attack the metal before C-C bond formation. Introduced herein is a rare nickel-based catalyst which promotes substitution with diarylmethane pronucleophiles by the soft-nucleophile pathway. Preliminary studies on the asymmetric allylic alkylation are promising. Just a softy: Contrary to what would be predicted, organosodium nucleophiles derived from diarylmethane pronucleophiles are shown to behave as soft nucleophiles in nickel-catalyzed allylic substitution reactions. This general reaction is demonstrated to proceed through a double inversion pathway. A promising asymmetric version is presented.
publishDate 2016
dc.date.none.fl_str_mv 2016-01-03
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/11336/51133
Sha, Sheng Chun; Jiang, Hui; Mao, Jianyou; Bellomo Peraza, Ana Ines; Jeong, Soo A.; et al.; Nickel-catalyzed allylic alkylation with diarylmethane pronucleophiles: Reaction development and mechanistic insights; Wiley VCH Verlag; Angewandte Chemie; 55; 3; 3-1-2016; 1070-1074
1433-7851
CONICET Digital
CONICET
url http://hdl.handle.net/11336/51133
identifier_str_mv Sha, Sheng Chun; Jiang, Hui; Mao, Jianyou; Bellomo Peraza, Ana Ines; Jeong, Soo A.; et al.; Nickel-catalyzed allylic alkylation with diarylmethane pronucleophiles: Reaction development and mechanistic insights; Wiley VCH Verlag; Angewandte Chemie; 55; 3; 3-1-2016; 1070-1074
1433-7851
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1002/anie.201507494
info:eu-repo/semantics/altIdentifier/url/https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.201507494
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 Wiley VCH Verlag
publisher.none.fl_str_mv Wiley VCH Verlag
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_ 1846082952489861120
score 13.22299

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