Palladium-catalyzed allylic substitution between C-based nucleophiles and 6-azabicyclo[3.1.0]-hex-3-en-2-oxy derivatives: A new selectivity paradigm

Detalhes bibliográficos
Autor(a) principal: Oliveira, João
Data de Publicação: 2020
Outros Autores: Kiala, Gredy, Siopa, Filipa, Bernard, Aurélie, Gontard, Geoffrey, Oble, Julie, Afonso, Carlos, Poli, Giovanni
Tipo de documento: Artigo
Idioma: eng
Título da fonte: Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)
Texto Completo: http://hdl.handle.net/10451/59203
Resumo: The reaction between α-hydroxy-(or α-acetoxy) cyclopenten-aziridines (6-azabicyclo[3.1.0]hex-3-en-2-ols or acetates) and C-based nucleophiles in the presence of Pd(0)-catalysis was investigated. In all the cases studied, the reaction was totally regio- and diastereo-selective, affording a single adduct in moderate to good yields. Specifically, attack of the nucleophile at position 3 of the cyclopentene moiety, anti to the vicinal oxy group, with vinylogous ring opening of the aziridine ring, was observed. When the carbon acid is a very acidic methylene (pKa (DMSO) ≤ 7.3), the resulting adduct is a zwitterion, resulting from an intramolecular proton transfer between the amino group and the carbon acid moiety taking place after the C–C bond formation. A plausible mechanism for this transformation is put forward.
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spelling Palladium-catalyzed allylic substitution between C-based nucleophiles and 6-azabicyclo[3.1.0]-hex-3-en-2-oxy derivatives: A new selectivity paradigmPalladium catalysisBicyclic aziridineTsuji-trost reactionThe reaction between α-hydroxy-(or α-acetoxy) cyclopenten-aziridines (6-azabicyclo[3.1.0]hex-3-en-2-ols or acetates) and C-based nucleophiles in the presence of Pd(0)-catalysis was investigated. In all the cases studied, the reaction was totally regio- and diastereo-selective, affording a single adduct in moderate to good yields. Specifically, attack of the nucleophile at position 3 of the cyclopentene moiety, anti to the vicinal oxy group, with vinylogous ring opening of the aziridine ring, was observed. When the carbon acid is a very acidic methylene (pKa (DMSO) ≤ 7.3), the resulting adduct is a zwitterion, resulting from an intramolecular proton transfer between the amino group and the carbon acid moiety taking place after the C–C bond formation. A plausible mechanism for this transformation is put forward.The authors would like to acknowledge Horizon 2020 ERANet-LAC project CelluloseSynThech for financial support (ref. ELAC2014/BEE-0341), as well as CNRS, Sorbonne Université and Labex Michem (Investissements d’Avenir programme, ref. ANR-11-IDEX-0004-02), Fundação para a Ciência e Tecnologia (SFRH/BPD/88666/2012, PTDC/QUI-QOR/32008/2017, UID/DTP/04138/2019) and COMPETE Programme (SAICTPAC/0019/2015). Support through CMST COST Action, CA15106 (CHAOS) is also gratefully acknowledged.ElsevierRepositório da Universidade de LisboaOliveira, JoãoKiala, GredySiopa, FilipaBernard, AurélieGontard, GeoffreyOble, JulieAfonso, CarlosPoli, Giovanni2023-09-11T15:29:20Z2020-042023-02-23T10:52:37Z2020-04-01T00:00:00Zinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10451/59203engOliveira JAC, Kiala G, Siopa F, Bernard A, Gontard G, Oble J, et al. Palladium-catalyzed allylic substitution between C-based nucleophiles and 6-azabicyclo[3.1.0]-hex-3-en-2-oxy derivatives: A new selectivity paradigm. Tetrahedron [Internet]. 18 de dezembro de 2020;76(51):131182. Disponível em: https://www.sciencedirect.com/science/article/pii/S00404020203031730040-4020cv-prod-175843810.1016/j.tet.2020.131182metadata only accessinfo:eu-repo/semantics/openAccessreponame:Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)instname:Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãoinstacron:RCAAP2023-11-08T17:03:58Zoai:repositorio.ul.pt:10451/59203Portal AgregadorONGhttps://www.rcaap.pt/oai/openaireopendoar:71602024-03-19T22:06:56.903359Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãofalse
dc.title.none.fl_str_mv Palladium-catalyzed allylic substitution between C-based nucleophiles and 6-azabicyclo[3.1.0]-hex-3-en-2-oxy derivatives: A new selectivity paradigm
title Palladium-catalyzed allylic substitution between C-based nucleophiles and 6-azabicyclo[3.1.0]-hex-3-en-2-oxy derivatives: A new selectivity paradigm
spellingShingle Palladium-catalyzed allylic substitution between C-based nucleophiles and 6-azabicyclo[3.1.0]-hex-3-en-2-oxy derivatives: A new selectivity paradigm
Oliveira, João
Palladium catalysis
Bicyclic aziridine
Tsuji-trost reaction
title_short Palladium-catalyzed allylic substitution between C-based nucleophiles and 6-azabicyclo[3.1.0]-hex-3-en-2-oxy derivatives: A new selectivity paradigm
title_full Palladium-catalyzed allylic substitution between C-based nucleophiles and 6-azabicyclo[3.1.0]-hex-3-en-2-oxy derivatives: A new selectivity paradigm
title_fullStr Palladium-catalyzed allylic substitution between C-based nucleophiles and 6-azabicyclo[3.1.0]-hex-3-en-2-oxy derivatives: A new selectivity paradigm
title_full_unstemmed Palladium-catalyzed allylic substitution between C-based nucleophiles and 6-azabicyclo[3.1.0]-hex-3-en-2-oxy derivatives: A new selectivity paradigm
title_sort Palladium-catalyzed allylic substitution between C-based nucleophiles and 6-azabicyclo[3.1.0]-hex-3-en-2-oxy derivatives: A new selectivity paradigm
author Oliveira, João
author_facet Oliveira, João
Kiala, Gredy
Siopa, Filipa
Bernard, Aurélie
Gontard, Geoffrey
Oble, Julie
Afonso, Carlos
Poli, Giovanni
author_role author
author2 Kiala, Gredy
Siopa, Filipa
Bernard, Aurélie
Gontard, Geoffrey
Oble, Julie
Afonso, Carlos
Poli, Giovanni
author2_role author
author
author
author
author
author
author
dc.contributor.none.fl_str_mv Repositório da Universidade de Lisboa
dc.contributor.author.fl_str_mv Oliveira, João
Kiala, Gredy
Siopa, Filipa
Bernard, Aurélie
Gontard, Geoffrey
Oble, Julie
Afonso, Carlos
Poli, Giovanni
dc.subject.por.fl_str_mv Palladium catalysis
Bicyclic aziridine
Tsuji-trost reaction
topic Palladium catalysis
Bicyclic aziridine
Tsuji-trost reaction
description The reaction between α-hydroxy-(or α-acetoxy) cyclopenten-aziridines (6-azabicyclo[3.1.0]hex-3-en-2-ols or acetates) and C-based nucleophiles in the presence of Pd(0)-catalysis was investigated. In all the cases studied, the reaction was totally regio- and diastereo-selective, affording a single adduct in moderate to good yields. Specifically, attack of the nucleophile at position 3 of the cyclopentene moiety, anti to the vicinal oxy group, with vinylogous ring opening of the aziridine ring, was observed. When the carbon acid is a very acidic methylene (pKa (DMSO) ≤ 7.3), the resulting adduct is a zwitterion, resulting from an intramolecular proton transfer between the amino group and the carbon acid moiety taking place after the C–C bond formation. A plausible mechanism for this transformation is put forward.
publishDate 2020
dc.date.none.fl_str_mv 2020-04
2020-04-01T00:00:00Z
2023-09-11T15:29:20Z
2023-02-23T10:52:37Z
dc.type.status.fl_str_mv info:eu-repo/semantics/publishedVersion
dc.type.driver.fl_str_mv info:eu-repo/semantics/article
format article
status_str publishedVersion
dc.identifier.uri.fl_str_mv http://hdl.handle.net/10451/59203
url http://hdl.handle.net/10451/59203
dc.language.iso.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv Oliveira JAC, Kiala G, Siopa F, Bernard A, Gontard G, Oble J, et al. Palladium-catalyzed allylic substitution between C-based nucleophiles and 6-azabicyclo[3.1.0]-hex-3-en-2-oxy derivatives: A new selectivity paradigm. Tetrahedron [Internet]. 18 de dezembro de 2020;76(51):131182. Disponível em: https://www.sciencedirect.com/science/article/pii/S0040402020303173
0040-4020
cv-prod-1758438
10.1016/j.tet.2020.131182
dc.rights.driver.fl_str_mv metadata only access
info:eu-repo/semantics/openAccess
rights_invalid_str_mv metadata only access
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv Elsevier
publisher.none.fl_str_mv Elsevier
dc.source.none.fl_str_mv reponame:Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)
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repository.name.fl_str_mv Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação
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