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Doctoral Thesis
DOI
10.11606/T.46.2005.tde-27082008-073450
Document
Author
Full name
Rodrigo Luiz Oliveira Rodrigues Cunha
E-mail
Institute/School/College
Knowledge Area
Date of Defense
Published
São Paulo, 2005
Supervisor
Committee
Comasseto, João Valdir (President)
Pilli, Ronaldo Aloise
Stefani, Hélio Alexandre
Tersariol, Ivarne Luís dos Santos
Vitta, Cláudio di
Title in Portuguese
Novos aspectos e aplicações da química de teluranas e de teluretos orgânicos
Keywords in Portuguese
Aziridinas
Catepsina B
Cnética enzimática
Compostos organometálicos
Cupratos
Heterociclos
Inibidores enzimáticos
Proteases
Reação de adição eletrofílica
Substituição eletrofílica aromática
Teluretos vinílicos
Telúrio
Tetracloreto de telúrio
Abstract in Portuguese
A primeira parte desta tese aborda estudos sobre a reatividade de compostos de telúrio eletrofílicos, principalmente tetracloreto de telúrio e tricloretos aromáticos de telúrio. Novos aspectos da reatividade de TeCl4 frente a alcinos e algumas acetofenonas foram observados e, a partir da elucidação estrutural dos compostos obtidos, por cristalografia, uma racionalização mecanística foi proposta para cada caso. As proposições apresentadas encontraram respaldo com a detecção de intermediários transientes por estudos de espectrometria de massas com ionização por electron-spray (ESI-MS/MS). Além de novos aspectos da química do Telúrio, os compostos preparados encontraram aplicação como potentes e seletivos inibidores de cisteíno proteases. Com esta aplicação estabelecida, foram sintetizadas ambos os enantiômeros de uma telurana e a atividade inibitória destas frente a Catepsina B mostrou dependência da estereoquímica devido a dependência estereoquímica da interação entre a enzima e o inibidor. A segunda parte deste trabalho trata do desenvolvimento da reação de abertura de anel de aziridinas por reagentes organometálicos de cobre derivados de teluretos vinílicos e arílicos que resultaram em derivados de aminas homoalílicas ou homobenzílicas. Em seguida, a reatividade de aziridinas alílicas foi estudada frente a uma série de reagentes organometálicos de lítio, magnésio, cobre e zinco que mostraram influenciar a regio- e estereosseletividades das reações de abertura.
Title in English
New aspects and applications of the chemistry of organotelluranes and organic tellurides
Keywords in English
Aziridines
Cathepsin B
Electrophilic aromatic substitution
Eletrophilic addition reaction
Enzymatic inhibitors
Enzymatic kinetics
Heterocycles
Organocuprates
Organometallic compounds
Proteases
Tellurium
Tellurium tetrachloride
Vinylic tellurides
Abstract in English
The first part of this thesis deals with the study of the reactivity of electrophilic tellurium compounds, mainly tellurium tetrachloride and aromatic tellurium trichlorides. New aspects of the reactivity of TeCl4 towards alkynes and some acetophenones were disclosed. A mechanistic rationale for each of the processes studied was possible by the determination of the stereochemistry for each product by monocrystal X-ray diffraction analysis. The proposition of the formation of cationic intermediates in the addition reaction of TeCl4 to alkynes was corroborated by the detection and characterization of transient intermediates by ESI-MS/MS experiments. Besides the new aspects of the Tellurium chemistry found, the prepared compounds showed a high and selective activity as inhibitors of cysteine proteases. A pair of enantiomers of a tellurane showed different activities against Human Catepsin B due to a stereochemical dependence in the enzyme/inhibitor interaction. The second part of the present work deals with the development of the ring opening reaction of aziridines by organometallic reagents of copper prepared from vinylic and arylic tellurides. These reactions led to homoallylic and homobenzylic amine derivatives. Finally, the reactivity of 2-alkenyl aziridines was studied towards a series of organometallic reagents of lithium, magnesium, copper and zinc which biased the regio- and stereoselectivities of the ring opening reactions.
 
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TeseRodrigoLORC.pdf (4.32 Mbytes)
Publishing Date
2008-09-04
 
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