Enantioselective protecting group-free synthesis of 1-S-ethyl-4-substituted quinolizidines

A practical enantioselective protecting group-free four-step route to the key quinolizidinone 6 from phenylglycinol-derived bicyclic lactam 1 is reported. The Grignard addition reaction to 6 takes place stereoselectively to give 1-ethyl-4-substituted quinolizidines 4-epi-207I and 7-9. Following a si...

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Autores: Amat Tusón, Mercedes, Semak, Vladislav, Escolano Mirón, Carmen, Molins i Grau, Elies, Bosch Cartes, Joan
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2012
País:España
Institución:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
Repositorio:Recercat. Dipósit de la Recerca de Catalunya
OAI Identifier:oai:recercat.cat:2445/127646
Acceso en línea:https://hdl.handle.net/2445/127646
Access Level:acceso abierto
Palabra clave:Alcaloides
Síntesi asimètrica
Síntesi orgànica
Compostos bioactius
Alkaloids
Asymmetric synthesis
Organic synthesis
Bioactive compounds
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spelling Enantioselective protecting group-free synthesis of 1-S-ethyl-4-substituted quinolizidinesAmat Tusón, MercedesSemak, VladislavEscolano Mirón, CarmenMolins i Grau, EliesBosch Cartes, JoanAlcaloidesSíntesi asimètricaSíntesi orgànicaCompostos bioactiusAlkaloidsAsymmetric synthesisOrganic synthesisBioactive compoundsA practical enantioselective protecting group-free four-step route to the key quinolizidinone 6 from phenylglycinol-derived bicyclic lactam 1 is reported. The Grignard addition reaction to 6 takes place stereoselectively to give 1-ethyl-4-substituted quinolizidines 4-epi-207I and 7-9. Following a similar synthetic sequence, 9a-epi-6 is also accessed. However, the addition of Grignard reagents to 9a-epi-6 proceeds in a non-stereoselective manner. In order to gain insight into the different stereochemical outcome in the two series, theoretical calculations on the iminium salts A and B have been performed. The study concludes that the addition of the hydride, which is the step that determines the configuration of the final products, occurs in a stereoelectronic controlled manner. The theoretical study is in agreement with the experimental results.Royal Society of Chemistry2019201920122019info:eu-repo/semantics/articleinfo:eu-repo/semantics/acceptedVersion10 p.application/pdfapplication/pdfhttps://hdl.handle.net/2445/127646Articles publicats en revistes (Farmacologia, Toxicologia i Química Terapèutica)reponame:Recercat. Dipósit de la Recerca de Catalunyainstname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)InglésVersió postprint del document publicat a: https://doi.org/10.1039/C2OB25392EOrganic & Biomolecular Chemistry, 2012, vol. 10, p. 6866-6875https://doi.org/10.1039/C2OB25392E(c) Amat Tusón, Mercedes et al., 2012info:eu-repo/semantics/openAccessoai:recercat.cat:2445/1276462026-05-29T05:05:01Z
dc.title.none.fl_str_mv Enantioselective protecting group-free synthesis of 1-S-ethyl-4-substituted quinolizidines
title Enantioselective protecting group-free synthesis of 1-S-ethyl-4-substituted quinolizidines
spellingShingle Enantioselective protecting group-free synthesis of 1-S-ethyl-4-substituted quinolizidines
Amat Tusón, Mercedes
Alcaloides
Síntesi asimètrica
Síntesi orgànica
Compostos bioactius
Alkaloids
Asymmetric synthesis
Organic synthesis
Bioactive compounds
title_short Enantioselective protecting group-free synthesis of 1-S-ethyl-4-substituted quinolizidines
title_full Enantioselective protecting group-free synthesis of 1-S-ethyl-4-substituted quinolizidines
title_fullStr Enantioselective protecting group-free synthesis of 1-S-ethyl-4-substituted quinolizidines
title_full_unstemmed Enantioselective protecting group-free synthesis of 1-S-ethyl-4-substituted quinolizidines
title_sort Enantioselective protecting group-free synthesis of 1-S-ethyl-4-substituted quinolizidines
dc.creator.none.fl_str_mv Amat Tusón, Mercedes
Semak, Vladislav
Escolano Mirón, Carmen
Molins i Grau, Elies
Bosch Cartes, Joan
author Amat Tusón, Mercedes
author_facet Amat Tusón, Mercedes
Semak, Vladislav
Escolano Mirón, Carmen
Molins i Grau, Elies
Bosch Cartes, Joan
author_role author
author2 Semak, Vladislav
Escolano Mirón, Carmen
Molins i Grau, Elies
Bosch Cartes, Joan
author2_role author
author
author
author
dc.subject.none.fl_str_mv Alcaloides
Síntesi asimètrica
Síntesi orgànica
Compostos bioactius
Alkaloids
Asymmetric synthesis
Organic synthesis
Bioactive compounds
topic Alcaloides
Síntesi asimètrica
Síntesi orgànica
Compostos bioactius
Alkaloids
Asymmetric synthesis
Organic synthesis
Bioactive compounds
description A practical enantioselective protecting group-free four-step route to the key quinolizidinone 6 from phenylglycinol-derived bicyclic lactam 1 is reported. The Grignard addition reaction to 6 takes place stereoselectively to give 1-ethyl-4-substituted quinolizidines 4-epi-207I and 7-9. Following a similar synthetic sequence, 9a-epi-6 is also accessed. However, the addition of Grignard reagents to 9a-epi-6 proceeds in a non-stereoselective manner. In order to gain insight into the different stereochemical outcome in the two series, theoretical calculations on the iminium salts A and B have been performed. The study concludes that the addition of the hydride, which is the step that determines the configuration of the final products, occurs in a stereoelectronic controlled manner. The theoretical study is in agreement with the experimental results.
publishDate 2012
dc.date.none.fl_str_mv 2012
2019
2019
2019
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/acceptedVersion
format article
status_str acceptedVersion
dc.identifier.none.fl_str_mv https://hdl.handle.net/2445/127646
url https://hdl.handle.net/2445/127646
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv Versió postprint del document publicat a: https://doi.org/10.1039/C2OB25392E
Organic & Biomolecular Chemistry, 2012, vol. 10, p. 6866-6875
https://doi.org/10.1039/C2OB25392E
dc.rights.none.fl_str_mv (c) Amat Tusón, Mercedes et al., 2012
info:eu-repo/semantics/openAccess
rights_invalid_str_mv (c) Amat Tusón, Mercedes et al., 2012
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv 10 p.
application/pdf
application/pdf
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 Articles publicats en revistes (Farmacologia, Toxicologia i Química Terapèutica)
reponame:Recercat. Dipósit de la Recerca de Catalunya
instname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
instname_str Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
reponame_str Recercat. Dipósit de la Recerca de Catalunya
collection Recercat. Dipósit de la Recerca de Catalunya
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15.811543

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