Reactivity of steroidal 1-azadienes toward enamines: an approach to novel chiral penta- and hexacyclic steroids

Detalhes bibliográficos
Autor(a) principal: Lopes, Susana M. M.
Data de Publicação: 2021
Outros Autores: Santos, Joana R. C., Pinho e Melo, Teresa M. V. D.
Tipo de documento: Artigo
Idioma: eng
Título da fonte: Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)
DOI: 10.1039/d0ob02344b
Texto Completo: http://hdl.handle.net/10316/107442
https://doi.org/10.1039/d0ob02344b
Resumo: The chemical behavior of steroidal N-sulfonyl-1-azadienes toward carbonyl compounds, in the presence of pyrrolidine, is described. With aldehydes, these azadienes participate in hetero-Diels-Alder reactions with the in situ generated enamines. The stereoselectivity results from the approach of the dienophiles from the less hindered α-face of the steroid, with the pyrrolidine moiety endo and retention of the enamine trans geometry. This diastereoselective synthetic methodology led to a new class of chiral pentacyclic steroids. Interestingly, the studied steroidal scaffolds follow a different mechanistic pathway with cyclic ketones. They undergo a diastereoselective annulation reaction, under enamine catalysis, affording chiral hexacyclic steroids.
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spelling Reactivity of steroidal 1-azadienes toward enamines: an approach to novel chiral penta- and hexacyclic steroidsAlkenesAminesAza CompoundsCatalysisModels, MolecularMolecular ConformationStereoisomerismSteroidsThe chemical behavior of steroidal N-sulfonyl-1-azadienes toward carbonyl compounds, in the presence of pyrrolidine, is described. With aldehydes, these azadienes participate in hetero-Diels-Alder reactions with the in situ generated enamines. The stereoselectivity results from the approach of the dienophiles from the less hindered α-face of the steroid, with the pyrrolidine moiety endo and retention of the enamine trans geometry. This diastereoselective synthetic methodology led to a new class of chiral pentacyclic steroids. Interestingly, the studied steroidal scaffolds follow a different mechanistic pathway with cyclic ketones. They undergo a diastereoselective annulation reaction, under enamine catalysis, affording chiral hexacyclic steroids.Royal Society of Chemistry2021-02-11info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articlehttp://hdl.handle.net/10316/107442http://hdl.handle.net/10316/107442https://doi.org/10.1039/d0ob02344bengLopes, Susana M. M.Santos, Joana R. C.Pinho e Melo, Teresa M. V. D.info: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:RCAAP2023-07-17T08:45:50Zoai:estudogeral.uc.pt:10316/107442Portal AgregadorONGhttps://www.rcaap.pt/oai/openaireopendoar:71602024-03-19T21:23:47.943973Repositório 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 Reactivity of steroidal 1-azadienes toward enamines: an approach to novel chiral penta- and hexacyclic steroids
title Reactivity of steroidal 1-azadienes toward enamines: an approach to novel chiral penta- and hexacyclic steroids
spellingShingle Reactivity of steroidal 1-azadienes toward enamines: an approach to novel chiral penta- and hexacyclic steroids
Reactivity of steroidal 1-azadienes toward enamines: an approach to novel chiral penta- and hexacyclic steroids
Lopes, Susana M. M.
Alkenes
Amines
Aza Compounds
Catalysis
Models, Molecular
Molecular Conformation
Stereoisomerism
Steroids
Lopes, Susana M. M.
Alkenes
Amines
Aza Compounds
Catalysis
Models, Molecular
Molecular Conformation
Stereoisomerism
Steroids
title_short Reactivity of steroidal 1-azadienes toward enamines: an approach to novel chiral penta- and hexacyclic steroids
title_full Reactivity of steroidal 1-azadienes toward enamines: an approach to novel chiral penta- and hexacyclic steroids
title_fullStr Reactivity of steroidal 1-azadienes toward enamines: an approach to novel chiral penta- and hexacyclic steroids
Reactivity of steroidal 1-azadienes toward enamines: an approach to novel chiral penta- and hexacyclic steroids
title_full_unstemmed Reactivity of steroidal 1-azadienes toward enamines: an approach to novel chiral penta- and hexacyclic steroids
Reactivity of steroidal 1-azadienes toward enamines: an approach to novel chiral penta- and hexacyclic steroids
title_sort Reactivity of steroidal 1-azadienes toward enamines: an approach to novel chiral penta- and hexacyclic steroids
author Lopes, Susana M. M.
author_facet Lopes, Susana M. M.
Lopes, Susana M. M.
Santos, Joana R. C.
Pinho e Melo, Teresa M. V. D.
Santos, Joana R. C.
Pinho e Melo, Teresa M. V. D.
author_role author
author2 Santos, Joana R. C.
Pinho e Melo, Teresa M. V. D.
author2_role author
author
dc.contributor.author.fl_str_mv Lopes, Susana M. M.
Santos, Joana R. C.
Pinho e Melo, Teresa M. V. D.
dc.subject.por.fl_str_mv Alkenes
Amines
Aza Compounds
Catalysis
Models, Molecular
Molecular Conformation
Stereoisomerism
Steroids
topic Alkenes
Amines
Aza Compounds
Catalysis
Models, Molecular
Molecular Conformation
Stereoisomerism
Steroids
description The chemical behavior of steroidal N-sulfonyl-1-azadienes toward carbonyl compounds, in the presence of pyrrolidine, is described. With aldehydes, these azadienes participate in hetero-Diels-Alder reactions with the in situ generated enamines. The stereoselectivity results from the approach of the dienophiles from the less hindered α-face of the steroid, with the pyrrolidine moiety endo and retention of the enamine trans geometry. This diastereoselective synthetic methodology led to a new class of chiral pentacyclic steroids. Interestingly, the studied steroidal scaffolds follow a different mechanistic pathway with cyclic ketones. They undergo a diastereoselective annulation reaction, under enamine catalysis, affording chiral hexacyclic steroids.
publishDate 2021
dc.date.none.fl_str_mv 2021-02-11
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/10316/107442
http://hdl.handle.net/10316/107442
https://doi.org/10.1039/d0ob02344b
url http://hdl.handle.net/10316/107442
https://doi.org/10.1039/d0ob02344b
dc.language.iso.fl_str_mv eng
language eng
dc.rights.driver.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.publisher.none.fl_str_mv Royal Society of Chemistry
publisher.none.fl_str_mv Royal Society of Chemistry
dc.source.none.fl_str_mv reponame:Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)
instname:Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação
instacron:RCAAP
instname_str Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação
instacron_str RCAAP
institution RCAAP
reponame_str Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)
collection Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)
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
repository.mail.fl_str_mv
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dc.identifier.doi.none.fl_str_mv 10.1039/d0ob02344b

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