Tris(triphenylphosphine)Ruthenium(II) dichloride: a versatile catalystin the synthesis of β-, γ- and δ-lactams from trichloroacetamides and in the isomerization of protected allylamines to Z-enamines under microwave activation

[eng] In this PhD thesis we have demonstrated that tris(triphenylphosphine)ruthenium(II) dichloride (RuCl2(PPh3)3) is a potent and versatile catalyst capable of achieving efficient different chemical transformations under microwave activation. In the first part of this PhD thesis, we have reported a...

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Autor: Șandor, Alexandra Georgiana
Tipo de recurso: tesis doctoral
Estado:Versión publicada
Fecha de publicación:2021
País:España
Institución:Universidad de Barcelona
Repositorio:Dipòsit Digital de la UB
OAI Identifier:oai:diposit.ub.edu:2445/185566
Acceso en línea:https://hdl.handle.net/2445/185566
http://hdl.handle.net/10803/674229
Access Level:acceso abierto
Palabra clave:Química orgànica
Compostos heterocíclics
Radicals lliures (Química)
Estructura molecular
Organic chemistry
Heterocyclic compounds
Free radicals (Chemistry)
Molecular structure
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network_acronym_str ES
network_name_str España
repository_id_str
dc.title.none.fl_str_mv Tris(triphenylphosphine)Ruthenium(II) dichloride: a versatile catalystin the synthesis of β-, γ- and δ-lactams from trichloroacetamides and in the isomerization of protected allylamines to Z-enamines under microwave activation
title Tris(triphenylphosphine)Ruthenium(II) dichloride: a versatile catalystin the synthesis of β-, γ- and δ-lactams from trichloroacetamides and in the isomerization of protected allylamines to Z-enamines under microwave activation
spellingShingle Tris(triphenylphosphine)Ruthenium(II) dichloride: a versatile catalystin the synthesis of β-, γ- and δ-lactams from trichloroacetamides and in the isomerization of protected allylamines to Z-enamines under microwave activation
Șandor, Alexandra Georgiana
Química orgànica
Compostos heterocíclics
Radicals lliures (Química)
Estructura molecular
Organic chemistry
Heterocyclic compounds
Free radicals (Chemistry)
Molecular structure
title_short Tris(triphenylphosphine)Ruthenium(II) dichloride: a versatile catalystin the synthesis of β-, γ- and δ-lactams from trichloroacetamides and in the isomerization of protected allylamines to Z-enamines under microwave activation
title_full Tris(triphenylphosphine)Ruthenium(II) dichloride: a versatile catalystin the synthesis of β-, γ- and δ-lactams from trichloroacetamides and in the isomerization of protected allylamines to Z-enamines under microwave activation
title_fullStr Tris(triphenylphosphine)Ruthenium(II) dichloride: a versatile catalystin the synthesis of β-, γ- and δ-lactams from trichloroacetamides and in the isomerization of protected allylamines to Z-enamines under microwave activation
title_full_unstemmed Tris(triphenylphosphine)Ruthenium(II) dichloride: a versatile catalystin the synthesis of β-, γ- and δ-lactams from trichloroacetamides and in the isomerization of protected allylamines to Z-enamines under microwave activation
title_sort Tris(triphenylphosphine)Ruthenium(II) dichloride: a versatile catalystin the synthesis of β-, γ- and δ-lactams from trichloroacetamides and in the isomerization of protected allylamines to Z-enamines under microwave activation
dc.creator.none.fl_str_mv Șandor, Alexandra Georgiana
author Șandor, Alexandra Georgiana
author_facet Șandor, Alexandra Georgiana
author_role author
dc.contributor.none.fl_str_mv Diaba, Faïza
Universitat de Barcelona. Facultat de Farmàcia i Ciències de l'Alimentació
dc.subject.none.fl_str_mv Química orgànica
Compostos heterocíclics
Radicals lliures (Química)
Estructura molecular
Organic chemistry
Heterocyclic compounds
Free radicals (Chemistry)
Molecular structure
topic Química orgànica
Compostos heterocíclics
Radicals lliures (Química)
Estructura molecular
Organic chemistry
Heterocyclic compounds
Free radicals (Chemistry)
Molecular structure
description [eng] In this PhD thesis we have demonstrated that tris(triphenylphosphine)ruthenium(II) dichloride (RuCl2(PPh3)3) is a potent and versatile catalyst capable of achieving efficient different chemical transformations under microwave activation. In the first part of this PhD thesis, we have reported an expeditious synthesis of β--lactams from N-tethered benzyl trichloroacetamides in the presence of RuCl2(PPh3)3and under microwave activation. The new C(sp3)-C(sp3) bond formation takes place through an unprecedented “Ru”complex promoted activation of a benzylic position in a radical process. The methodology was applied on 10 examples with acceptable yields considering the challenging C-C bond formed in this radical process. Of the β-lactams prepared, 6 were analyzed for their cytotoxic activity and hemocompatibility. The results obtained showed that these lactams have non-hemolytic character and that their cytotoxic response is highly dependent on their structural characteristics and their concentration. One of the compounds tested was found to be the most cytotoxic showing the lowest IC50 values. In the second part of the thesis, we have reported the first isomerization of tertiary allylcarbamates and allylamides to the corresponding Z-enecarbamates and Z-enamides in the presence of RuCl2(PPh3)3as a catalyst with very good yieldsand excellent Z-selectivity. The reactions are achieved under microwave activation and in very short reaction time on different substrates. In this transformation we have demonstrated that the nature of the protective group on the nitrogen is decisive tothe course of the reaction. Finally, the same catalyst was used for the synthesis of γ-and δ-lactams from N-tethered alkenyl trichloroacetamides. In this part of the work, a reliable diastereoselective Atom Transfer Radical Cyclization takes place in thepresence of a catalytic amount of RuCl2(PPh3)3to provide the corresponding lactams with good yields. The methodology was successfully used for a diastereoselective synthesis of functionalized indole and morphan scaffolds present in many natural compoundssuch as the Daphniphyllumalkaloids.
publishDate 2021
dc.date.none.fl_str_mv 2021
dc.type.none.fl_str_mv info:eu-repo/semantics/doctoralThesis
info:eu-repo/semantics/publishedVersion
format doctoralThesis
status_str publishedVersion
dc.identifier.none.fl_str_mv https://hdl.handle.net/2445/185566
http://hdl.handle.net/10803/674229
url https://hdl.handle.net/2445/185566
http://hdl.handle.net/10803/674229
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.rights.none.fl_str_mv (c) Șandor, Alexandra Georgiana, 2022
info:eu-repo/semantics/openAccess
rights_invalid_str_mv (c) Șandor, Alexandra Georgiana, 2022
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv Universitat de Barcelona
publisher.none.fl_str_mv Universitat de Barcelona
dc.source.none.fl_str_mv Tesis Doctorals - Facultat - Farmàcia i Ciències de l'Alimentació
reponame:Dipòsit Digital de la UB
instname:Universidad de Barcelona
instname_str Universidad de Barcelona
reponame_str Dipòsit Digital de la UB
collection Dipòsit Digital de la UB
repository.name.fl_str_mv
repository.mail.fl_str_mv
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spelling Tris(triphenylphosphine)Ruthenium(II) dichloride: a versatile catalystin the synthesis of β-, γ- and δ-lactams from trichloroacetamides and in the isomerization of protected allylamines to Z-enamines under microwave activationȘandor, Alexandra GeorgianaQuímica orgànicaCompostos heterocíclicsRadicals lliures (Química)Estructura molecularOrganic chemistryHeterocyclic compoundsFree radicals (Chemistry)Molecular structure[eng] In this PhD thesis we have demonstrated that tris(triphenylphosphine)ruthenium(II) dichloride (RuCl2(PPh3)3) is a potent and versatile catalyst capable of achieving efficient different chemical transformations under microwave activation. In the first part of this PhD thesis, we have reported an expeditious synthesis of β--lactams from N-tethered benzyl trichloroacetamides in the presence of RuCl2(PPh3)3and under microwave activation. The new C(sp3)-C(sp3) bond formation takes place through an unprecedented “Ru”complex promoted activation of a benzylic position in a radical process. The methodology was applied on 10 examples with acceptable yields considering the challenging C-C bond formed in this radical process. Of the β-lactams prepared, 6 were analyzed for their cytotoxic activity and hemocompatibility. The results obtained showed that these lactams have non-hemolytic character and that their cytotoxic response is highly dependent on their structural characteristics and their concentration. One of the compounds tested was found to be the most cytotoxic showing the lowest IC50 values. In the second part of the thesis, we have reported the first isomerization of tertiary allylcarbamates and allylamides to the corresponding Z-enecarbamates and Z-enamides in the presence of RuCl2(PPh3)3as a catalyst with very good yieldsand excellent Z-selectivity. The reactions are achieved under microwave activation and in very short reaction time on different substrates. In this transformation we have demonstrated that the nature of the protective group on the nitrogen is decisive tothe course of the reaction. Finally, the same catalyst was used for the synthesis of γ-and δ-lactams from N-tethered alkenyl trichloroacetamides. In this part of the work, a reliable diastereoselective Atom Transfer Radical Cyclization takes place in thepresence of a catalytic amount of RuCl2(PPh3)3to provide the corresponding lactams with good yields. The methodology was successfully used for a diastereoselective synthesis of functionalized indole and morphan scaffolds present in many natural compoundssuch as the Daphniphyllumalkaloids.[spa] En esta tesis doctoral hemos demostrado que el cloruro de tris(trifenilfosfina)rutenio (II) (RuCl2(PPh3)3) es un catalizador versátil y eficiente para efectuar varias transformaciones químicas bajo activación por microondas.En la primera parte, hemos descrito un comportamiento sin precedentes del catalizador RuCl2(PPh3)3para la síntesis de β-lactamas a partir de N-bencil tricloroacetamidas. La formación del nuevo enlace C(sp3) -C(sp3) tiene lugar a través de la activación de un C-H bencílico promovida por un complejo de rutenio en un proceso radicalario. La metodología se aplicó a 10 sustratos diferentes con rendimientos aceptables considerando la complejidad del nuevo enlace C-C formado.De las β-lactamas preparadas, se analizaron 6 para determinar su actividad citotóxica y hemocompatibilidad. Los resultados obtenidos mostraron que estas lactamas tienen carácter no hemolítico y que su respuesta citotóxica es altamente dependiente de sus características estructurales y de su concentración. Uno de los compuestos mostró ser el más citotóxico con los valores de IC50 más bajos.En la segunda parte de la tesis hemos descrito la primera isomerización de alilcarbamatos y alilamidas terciariasa los correspondientes Z-enecarbamatos y Z-enamidas en presencia de RuCl2(PPh3)3como catalizador con muy buenos rendimientos y una excelente Z-selectividad. Las reacciones se llevaron a cabo bajo activación con microondas y en tiempos de reacción muy cortos sobre diferentes sustratos. En esta transformación hemos demostrado que la naturaleza del grupo protector en el nitrógeno resulta determinante para el curso de la reacción.Finalmente, RuCl2(PPh3)3fue empleado con éxito para la preparación de γ-y δ-lactamas a partir de N-alquenil tricloro y dichloroacetamidas. En esta reacción, una ciclación radicalaria con transferencia de átomo tiene lugar de manera diastereoselectiva en presencia de una cantidad catalítica del catalizador para proporcionar las lactamas correspondientes con buenos rendimientos. La metodología se ha empleado con éxito para una síntesis diastereoselectiva de índoles y morfanos funcionalizados presentes en muchos productos naturales como los alcaloides Daphniphyllum.Universitat de BarcelonaDiaba, FaïzaUniversitat de Barcelona. Facultat de Farmàcia i Ciències de l'Alimentació2021info:eu-repo/semantics/doctoralThesisinfo:eu-repo/semantics/publishedVersionapplication/pdfhttps://hdl.handle.net/2445/185566http://hdl.handle.net/10803/674229Tesis Doctorals - Facultat - Farmàcia i Ciències de l'Alimentacióreponame:Dipòsit Digital de la UBinstname:Universidad de BarcelonaInglés(c) Șandor, Alexandra Georgiana, 2022info:eu-repo/semantics/openAccessoai:diposit.ub.edu:2445/1855662026-05-27T06:46:51Z
score 15,301629

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