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Thèse de Doctorat
DOI
10.11606/T.46.2008.tde-25042008-103701
Document
Auteur
Nom complet
Rodrigo Cella
Adresse Mail
Unité de l'USP
Domain de Connaissance
Date de Soutenance
Editeur
São Paulo, 2008
Directeur
Jury
Stefani, Hélio Alexandre (Président)
Braga, Antônio Luiz
Marzorati, Liliana
Petragnani, Nicola
Schneider, Paulo Henrique
Titre en portugais
Estudo visando à síntese enantiosseletiva da malevamida D e reações de Suzuki-Miyaura envolvendo espécies insaturadas de telúrio
Mots-clés en portugais
Estereosseletividade
Malevamida D
Organotelúrio
Organotrifluoroborato
Paládio
Suzuki-Miyaura
Telúrio
Resumé en portugais
Esta tese descreve, em dois diferentes capítulos, a síntese assimétrica da Malevamida D e a aplicação de compostos organotelúrio em reações de Suzuki-Miyaura. O primeiro capítulo refere-se ao estudo da síntese assimétrica da Malevamida D, um depsipeptídeo natural pertencente à família das dolastatinas, compostos estes com grande atividade citotóxica. As unidades DAP e MMMAH foram alcançadas em ótimos redimentos e estereosseletividades, utilizando-se reações de adição de crotil ou aliltrifluoroborato de potássio à aldeídos derivados da L-prolina e L-isoleucina, respectivamente. A elongação da cadeia da malevamida D se fez a partir de reações de esterificação e amidação; infelizmente não foi possível completar a síntese devido a problemas na última reação de acoplamento peptídico. O segundo capítulo descreve as reações entre teluretos aromáticos ou vinílicos e sais de organotrifluoroborato de potássio, mediadas por um catalisador de paládio. A partir destas reações de acoplamento cruzado tipo Suzuki-Miyaura foi possível obter-se 1,3-eninos, sistemas biarílicos, (E)- ou (Z)-estilbenos e 1,3-dienos. Todas as reações mostraram serem tolerantes a uma grande variedade de grupos funcionais e altamente estereoconservativas, nos casos envolvendo substratos vinílicos.
Titre en anglais
Study towards to enantioselective synthesis of malevamide D and Suzuki-Miyaura reaction involving tellurium species
Mots-clés en anglais
Malevamide D
Organotellurium
Organotrifluoroborate
Stereoselectivity
Suzuki-Miyaura
Tellurium
Resumé en anglais
This thesis describes, in two different chapters, the asymmetric synthesis of malevamide D and the application of organotellurium compounds in Suzuki-Miyaura reaction. The first chapter refers to the asymmetric synthesis of malevamide D, a natural depsipeptide which belongs to the dolastatins family, and these compounds have a great interest due to theirs citotoxic activities. The DAP and MMMAH units were reached in excellent yields and stereoselectivities from 1,2-addition reaction of potassium crotyl or allyltrifluoroborate to aldehydes derivate from L-proline and L-isoleucine, respectively. The malevamide D elongation was made from reaction of esterification and amidation, unfortunately it was not possible finish the synthesis due to some problems in the last step of the total synthesis. The second chapter describes the reaction between aryl or vinyl tellurides and potassium organotrifluoroborate salts, mediated by a palladium catalyst. From this cross-coupling reaction type Suzuki-Miyaura was possible obtain 1,3-dienes, biarylic systems, (E)- or (Z)-stylbenes and 1,3-dienes. Al reactions showed to be tolerant to a wide range of functional groups and highly stereoconservative, in the cases involving vinylic substrates.
 
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ErrataRodrigoCella.pdf (31.49 Kbytes)
TeseRodrigoCella.pdf (4.15 Mbytes)
Date de Publication
2008-06-03
 
AVERTISSEMENT: Le matériau se réfère à des documents provenant de cette thèse ou mémoire. Le contenu de ces documents est la responsabilité de l'auteur de la thèse ou mémoire.
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