Total Synthesis of Phlegmarine Alkaloids

[eng] This doctoral thesis consists in two main parts. The first part focus in the study of methodology development in order to bring modularity and diversification to compounds studied within the research group. It consists first in the development of an easy procedure to access enantiopure substit...

Descripción completa

Detalles Bibliográficos
Autor: Bosch, Caroline
Tipo de recurso: tesis doctoral
Estado:Versión publicada
Fecha de publicación:2016
País:España
Institución:Universidad de Barcelona
Repositorio:Dipòsit Digital de la UB
OAI Identifier:oai:diposit.ub.edu:2445/106167
Acceso en línea:https://hdl.handle.net/2445/106167
http://hdl.handle.net/10803/399380
Access Level:acceso abierto
Palabra clave:Síntesi orgànica
Alcaloides
Organic synthesis
Alkaloids
id ES_e69f0b09f22e2ce9b0772dd0187da866
oai_identifier_str oai:diposit.ub.edu:2445/106167
network_acronym_str ES
network_name_str España
repository_id_str
spelling Total Synthesis of Phlegmarine AlkaloidsBosch, CarolineSíntesi orgànicaAlcaloidesOrganic synthesisAlkaloids[eng] This doctoral thesis consists in two main parts. The first part focus in the study of methodology development in order to bring modularity and diversification to compounds studied within the research group. It consists first in the development of an easy procedure to access enantiopure substituted octahydroindoles relevant for natural products synthesis, then in the diversification of a common building block used for the total synthesis of phlegmarine alkaloids allowing access to unprecedented heterocyclic tetrahydrocarbazoles compounds, but most importantly in the achievement of a methodology allowing access to any phlegmarine alkaloids from a simple common precursor i.e. using a unified methodology. A stereodivergent hydrogenation route is reported in each phlegmarine alkaloid series, allowing modulation of the diastereoselectivity in key intermediates of the synthetic approach. The second part focuses on synthetic applications of the methodology developed to allow to perform the first total synthesis of various phlegmarine alkaloids and also shed light on missassigned structures. These structure reassignments gave birth to a revised classification of the phlegmarine alkaloids and were confirmed by total synthesis using the unified methodology developed in the first part. All of the analytical data obtained during this project led us to the establishment of general rules to determine easily the stereochemistry of any phlegmarine type alkaloids. In summary, the first total syntheses of (+)-serratezomine E, (-)-serralongamine, (-)-huperzine K, huperzine M and (-)-huperzine N have been achieved and the usefulness of the tandem intermolecular Michael reaction/intramolecular aldol reaction and in-situ intramolecular aza-Michael process has been extended to other series of azabicyclic compounds in enantiopure form.Universitat de BarcelonaBonjoch i Sesé, JosepBradshaw, BenUniversitat de Barcelona. Departament de Farmacologia, Toxicologia i Química Terapèutica2016info:eu-repo/semantics/doctoralThesisinfo:eu-repo/semantics/publishedVersionapplication/pdfhttps://hdl.handle.net/2445/106167http://hdl.handle.net/10803/399380Tesis Doctorals - Departament - Farmacologia, Toxicologia i Química Terapèuticareponame:Dipòsit Digital de la UBinstname:Universidad de BarcelonaInglés(c) Bosch, 2016info:eu-repo/semantics/openAccessoai:diposit.ub.edu:2445/1061672026-05-27T06:46:51Z
dc.title.none.fl_str_mv Total Synthesis of Phlegmarine Alkaloids
title Total Synthesis of Phlegmarine Alkaloids
spellingShingle Total Synthesis of Phlegmarine Alkaloids
Bosch, Caroline
Síntesi orgànica
Alcaloides
Organic synthesis
Alkaloids
title_short Total Synthesis of Phlegmarine Alkaloids
title_full Total Synthesis of Phlegmarine Alkaloids
title_fullStr Total Synthesis of Phlegmarine Alkaloids
title_full_unstemmed Total Synthesis of Phlegmarine Alkaloids
title_sort Total Synthesis of Phlegmarine Alkaloids
dc.creator.none.fl_str_mv Bosch, Caroline
author Bosch, Caroline
author_facet Bosch, Caroline
author_role author
dc.contributor.none.fl_str_mv Bonjoch i Sesé, Josep
Bradshaw, Ben
Universitat de Barcelona. Departament de Farmacologia, Toxicologia i Química Terapèutica
dc.subject.none.fl_str_mv Síntesi orgànica
Alcaloides
Organic synthesis
Alkaloids
topic Síntesi orgànica
Alcaloides
Organic synthesis
Alkaloids
description [eng] This doctoral thesis consists in two main parts. The first part focus in the study of methodology development in order to bring modularity and diversification to compounds studied within the research group. It consists first in the development of an easy procedure to access enantiopure substituted octahydroindoles relevant for natural products synthesis, then in the diversification of a common building block used for the total synthesis of phlegmarine alkaloids allowing access to unprecedented heterocyclic tetrahydrocarbazoles compounds, but most importantly in the achievement of a methodology allowing access to any phlegmarine alkaloids from a simple common precursor i.e. using a unified methodology. A stereodivergent hydrogenation route is reported in each phlegmarine alkaloid series, allowing modulation of the diastereoselectivity in key intermediates of the synthetic approach. The second part focuses on synthetic applications of the methodology developed to allow to perform the first total synthesis of various phlegmarine alkaloids and also shed light on missassigned structures. These structure reassignments gave birth to a revised classification of the phlegmarine alkaloids and were confirmed by total synthesis using the unified methodology developed in the first part. All of the analytical data obtained during this project led us to the establishment of general rules to determine easily the stereochemistry of any phlegmarine type alkaloids. In summary, the first total syntheses of (+)-serratezomine E, (-)-serralongamine, (-)-huperzine K, huperzine M and (-)-huperzine N have been achieved and the usefulness of the tandem intermolecular Michael reaction/intramolecular aldol reaction and in-situ intramolecular aza-Michael process has been extended to other series of azabicyclic compounds in enantiopure form.
publishDate 2016
dc.date.none.fl_str_mv 2016
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/2445/106167
http://hdl.handle.net/10803/399380
url https://hdl.handle.net/2445/106167
http://hdl.handle.net/10803/399380
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.rights.none.fl_str_mv (c) Bosch, 2016
info:eu-repo/semantics/openAccess
rights_invalid_str_mv (c) Bosch, 2016
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 - Departament - Farmacologia, Toxicologia i Química Terapèutica
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
_version_ 1869422782618533888
score 15,301603

Similares en LA Referencia