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Previous issue date: 2012-05-04 / Conselho Nacional de Pesquisa e Desenvolvimento Científico e Tecnológico - CNPq / This work describes some studies on the preparation of unsymmetrical
diaryl thioethers catalyzed by Copper(I)-Senelenophene-2-carboxylate. The
results concern to the catalyzed cross-coupling reaction between aryl halides
and aryl or alkylthiols using Copper(I)-Senelenophene-2-carboxylate (CuSC) a
new Cu-catalyzed one-pot protocol. The products were obtained in good to
excellent yields under relatively mild reaction conditions presenting
chemoselectivity and functional group tolerance. Additionally, we have developed a chemio-, regio and stereoselective
synthesis of vinyl chalcogenides compounds promoted by zinc chalcogenolates.
In this protocol the reductive cleavage of chalcogen bond by the Zn/NH4OH
system led to zinc chalcogenolates. The reaction was carried out with acids and
esters propiolics afford β-chalcogenacrillic acids and esters under mild and
basic conditions. The stereochemistry corresponding to anti-Markovnikov
addition of the chalcogenolate constituents across the triple bond were obtained
in good yields. / Este trabalho descreve o estudo das reações de acoplamento cruzado
entre iodetos arílicos e tióis arílicos ou alquílicos catalisada por 2-carboxilato
selenofeno de cobre (I) (CuSC). Apresentamos uma nova metodologia “ one
pote” para a síntese de tioésteres arílicos obtidos em condições reacionais
relativamente brandas, apresentando quimiosseletividade, tolerância a diversos
grupos funcionais e rendimentos que variam entre bons a ótimos (70-100%).
R1I + R2SH
K3PO4, DMSO
S
R1 R2
Adicionalmente, desenvolvemos uma síntese quimio, régio, e
estereosseletiva de compostos vinil calcogenetos promovida por calcogenolato
de zinco. Neste protocolo a clivagem redutiva da ligação calcogênio feita pelo
sistema Zn/NH4OH obteve os calcogenolatos de zinco. A reação foi realizada
com ácidos e ésteres propiólicos formando ácidos acrílicos β-calcogênio e
ésteres sob condições básicas e brandas. A estereoquímica corresponde a
adição anti-Markovnikov dos constituintes calcogenolatos através da ligação
tripla. Os calcogenetos vinílicos foram obtidos em bons rendimentos (40-96).
| Identifer | oai:union.ndltd.org:IBICT/oai:repositorio.bc.ufg.br:tede/3097 |
| Date | 04 May 2012 |
| Creators | Nunes, Vanessa Loren |
| Contributors | Barros, Olga Soares do Rêgo, Barros, Olga Soares do Rêgo, Souza, Aparecido Ribeiro de, Vasconcellos, Mário Luiz Araújo de Almeida |
| Publisher | Universidade Federal de Goiás, Programa de Pós-graduação em Química (IQ), UFG, Brasil, Instituto de Química - IQ (RG) |
| Source Sets | IBICT Brazilian ETDs |
| Language | Portuguese |
| Detected Language | English |
| Type | info:eu-repo/semantics/publishedVersion, info:eu-repo/semantics/masterThesis |
| Format | application/pdf |
| Source | reponame:Biblioteca Digital de Teses e Dissertações da UFG, instname:Universidade Federal de Goiás, instacron:UFG |
| Rights | http://creativecommons.org/licenses/by-nc-nd/4.0/, info:eu-repo/semantics/openAccess |
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