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Doctoral Thesis
DOI
10.11606/T.46.2005.tde-26122006-110452
Document
Author
Full name
Cristiano Raminelli
E-mail
Institute/School/College
Knowledge Area
Date of Defense
Published
São Paulo, 2005
Supervisor
Committee
Comasseto, João Valdir (President)
Baader, Josef Wilhelm
Ferraz, Helena Maria Carvalho
Moran, Paulo José Samenho
Simonelli, Fábio
Title in Portuguese
Teluretos vinílicos em reações de acoplamento catalisadas por cloreto de paládio (II) ou complexos de níquel
Keywords in Portuguese
Catálise
Níquel
Paládio
Reações de acoplamento
Síntese orgânica
Teluretos vinílicos
Abstract in Portuguese
Nesta tese apresentamos um estudo sistemático da reação de alquinilação de teluretos Z-vinílicos promovida por PdCl2 e CuI. O sucesso de tal reação foi dependente da quantidade de PdCl2 empregado, por outro lado, o sal de cobre (I) não apresentou influência significativa sobre o curso da reação. Posteriormente, empregando PdCl2 em quantidades catalíticas, vários agentes oxidantes ou aditivos foram testados. No entanto, o resultado mais significativo foi obtido quando CuCl2 foi usado na presença de ar. Este resultado deu origem a uma nova metodologia para a alquinilação de teluretos Z-vinílicos, que emprega PdCl2 em quantidade catalítica e CuCl2 em excesso. Adicionalmente, um mecanismo para a reação desenvolvida foi proposto com base em experimentos realizados empregando espectroscopia de massas. Tendo em vista o alto custo dos reagentes de paládio, foram implementadas metodologias para promover a formação de ligações carbono-carbono, usando teluretos vinílicos e reagentes organometálicos na presença de quantidades catalíticas de complexos de níquel (II). Na última etapa do nosso trabalho, teluretos Z-vinílicos quirais foram sintetizados usando biocatálise como ferramenta, sendo posteriormente submetidos à reação de acoplamento resultando em álcoois enínicos de configuração Z quirais. A seqüência de reações foi testada inicialmente em sua versão racêmica.
Title in English
Vinylic tellurides in coupling reactions catalized by palladium (II) chloride or nickel complexes
Keywords in English
Catalysis
Coupling reactions
Nickel
Organic synthesis
Palladium
Vinylic tellurides
Abstract in English
In this thesis we report a systematic study concerning the alkynylation of Z-vinylic telurides promoted by PdCl2 and CuI. The performance of such reaction was dependent of the amount of PdCl2 employed. On the other hand, the copper (I) salt did not show significant influence in the course of the reaction. Afterwards, employing PdCl2 in catalytic amounts, several oxidizing agents or additives were tested. The most significant result was obtained when CuCl2 was used in the presence of air. This finding brought to light a new methodology for alkynylation of Z-vinylic telurides that employs catalytic amount of PdCl2 and CuCl2 excess. In addition, a mechanism for the new reaction has been proposed with basis in the data obtained by mass spectrometric experiments. In view of the high cost of the palladium reagents, we developed methodologies that promote the formation of carbon-carbon bonds by using vinylic tellurides and organometallic reagents in the presence of catalytic amounts of nickel (II) complexes. In the last stage of our work, chiral Z-vinylic tellurides were synthesized by using biocatalysis as a tool. After that, the chiral tellurides were submitted to the coupling reaction affording chiral enynic alcohos with Z configuration. The reaction sequence was tested initially in its racemic version.
 
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Tese_A.pdf (45.81 Kbytes)
Tese_B.pdf (1.05 Mbytes)
Tese_Ca.pdf (382.27 Kbytes)
Tese_Cb.pdf (439.02 Kbytes)
Tese_Cc.pdf (415.58 Kbytes)
Tese_Cd.pdf (277.92 Kbytes)
Publishing Date
2007-01-19
 
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