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Master's Dissertation
DOI
10.11606/D.9.2013.tde-22042013-143833
Document
Author
Full name
Nathalia Cristina da Silva e Silva
E-mail
Institute/School/College
Knowledge Area
Date of Defense
Published
São Paulo, 2013
Supervisor
Committee
Stefani, Helio Alexandre (President)
Santos, Alcindo Aparecido dos
Vieira, Adriano Siqueira
Title in Portuguese
Funcionalização do 3,4,6-tri-O-acetil-D-glucal com sais de organotrifluoroboratos de potássio e reações de click chemistry para a geração e funcionalização de triazóis
Keywords in Portuguese
Click chemistry
Insumos farmacêuticos
Organotrifluoroboratos
Troca Te/Li
Abstract in Portuguese
No presente trabalho, foi desenvolvida uma metodologia sintética para a funcionalização de um monossacarídeo derivado da D-glicose através do Rearranjo de Ferrier, utilizando-se um sal de organotrifluoroborato de potássio como nucleófilo. Em seguida, foi feita a reação de cicloadição azida-acetileno com cobre, através de estratégias simples e eficientes, que seguem a filosofia da click chemistry, permitindo a preparação de uma série de compostos com grande diversidade estrutural, possuindo dois anéis heterocíclicos e diversos substituintes, com promissora atividade biológica. Dando continuidade ao projeto, foi feita a metanólise dos grupamentos acetila, com carbonato de potássio e metanol. Assim, as novas moléculas adquirem maior hidrofilicidade e podem ser enviadas para novos testes biológicos, para fins de comparação com as anteriores. A partir dos compostos desprotegidos, foi feita a mesilação seletiva da hidroxila primária do açúcar e a substituição com selenolato de sódio, com a obtenção de seleno-carboidratos inéditos. Em uma segunda etapa do trabalho, exploramos a reatividade do núcleo triazólico, com a reação de troca Te/Li seguida de captura por eletrófilo. O material de partida foi sintetizado a partir do fenil acetileno. Com o triazol telurado em mãos, partimos para as reações de troca e captura por eletrófilo. Utilizamos diferentes tipos de eletrófilos, como aldeídos, cetonas, iodetos, dentre outros.
Title in English
Functionalization of 3,4,6-tri-O-acetyl-D-glucal with potassium organotrifluoroborate salts and click chemistry reactions for the generation and functionalization of triazoles.
Keywords in English
Click chemistry
Organotrifluoroborates
Pharmaceutical raw material
Te/Li exchange
Abstract in English
We developed a synthetic methodology for the functionalization of a monosaccharide derived from D-glucose, using the Ferrier rearrangement with a potassium organotrifluoroborate salt as the nucleophile. This way, a series of coumpounds with high structural diversity and two heterocyclic rings having different substituents were produced, using the azide-acetylene cycloaddition reaction. Through this simple and efficient methodology, that follows the "click chemistry" philosophy, we could synthesize molecules with promising biological activity. Continuing the project, we performed the methanolysis of the acetyl groups, with potassium carbonate and methanol. Thus, the new molecules become more hydrophilic and could be sent to new biological tests, for a comparison with the previous ones. From the deprotected compounds, we were able to mesilate the primary hydroxyl and substitute it with sodium selenolate, obtaining novel selenium-carbohydrates. In a second part of our work, we were able to exploit the triazole reactivity trough the Te/Li exchange reaction followed by the electrophile capture. The starting material was obtained from phenyl acetylene. With the teluratte in our hands, we set out to the exchange reactions, using several types of electrophiles, such as aldehydes, ketones, iodide, among others.
 
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DISSERTACAOFINAL.pdf (3.83 Mbytes)
Publishing Date
2013-09-25
 
WARNING: The material described below relates to works resulting from this thesis or dissertation. The contents of these works are the author's responsibility.
  • Stefani, Hélio A., et al. Functionalization of 5-telluro-1,2,3-triazoles: Te/Li exchange and Suzuki-Miyaura cross-coupling reaction [doi:10.1016/j.tetlet.2013.03.061]. Tetrahedron Letters [online], 2013, vol. 54, p. 2809-2812.
All rights of the thesis/dissertation are from the authors
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