Estudo da resolução cinética dinâmica de aminas primárias com catalisador de paládio suportado em dolomita
Data
2023-10-19
Autores
Boaretto, Matheus 
Orientadores
Siqueira, Fernanda Amaral de
Tipo
Trabalho de conclusão de curso
Título da Revista
ISSN da Revista
Título de Volume
Resumo
O objetivo principal deste trabalho é estudar a metodologia de Resolução Cinética Dinâmica (RCD) de aminas primárias com o uso de catalisador de paládio suportado em dolomita, o qual foi desenvolvido pelo grupo de pesquisa. A RCD é uma metodologia utilizada para a síntese enantiosseletiva a partir de uma mistura racêmica. Nessa técnica são utilizados dois catalisadores, sendo um enzimático (Lipase Candida antarctica B - CaLB) que possui preferência pelo enantiômero R, e o outro metálico que racemiza o enantiômero indesejado tornando-o hábil para reagir novamente e gerar o enantiômero desejado em maiores proporções. Para o estudo foi selecionada a classe das aminas, pois possuem grande importância na síntese de diversos fármacos e na indústria agroquímica. O catalisador metálico é paládio suportado em dolomita, que apresentou boas conversões e bons excessos enantioméricos. Na tentativa de aprimorar essa metodologia foram utilizados líquidos iônicos do tipo triflatos de amônio e fosfônio (N4444.NTf2, P4444.NTf2, N8888.NTf2 e P8888.NTf2), os quais, podem estabilizar as nanopartículas de paládio, evitando sua aglomeração e consequente perda da atividade catalítica. Esses líquidos iônicos foram desenvolvidos pelo grupo de pesquisa do professor Luiz Longo, com quem estabelecemos uma parceria. Também foram realizados testes com os substratos (R,S)1-(4-fluoro)feniletilamina e (R,S)- 1,2,3,4-tetra-hidro 1-naftilamina com os líquidos iônicos citados com o objetivo de ampliar o escopo da metodologia de RCD.
The main objective of this work is to study the methodology of Dynamic Kinetic Resolution (DKR) of primary amines using a palladium catalyst supported on dolomite, which was developed by the research group. DKR is a methodology used for the enantioselective synthesis from a racemic mixture. In this technique, two catalysts are used, one being enzymatic (Lipase Candida antarctica B - CaLB) which has a preference for the R enantiomer, and the other metallic which racemizes the unwanted enantiomer making it able to react again and generate the desired enantiomer in greater proportions. For the study, the class of amines was selected, as they are of great importance in the synthesis of various drugs and in the agrochemical industry. The metallic catalyst is palladium supported on dolomite, which showed good conversions and good enantiomeric excesses. In an attempt to improve this methodology, ionic liquids such as ammonium and phosphonium triflates (N4444.NTf2, P4444.NTf2, N8888.NTf2 and P8888.NTf2) were used, which can stabilize palladium nanoparticles, preventing their agglomeration and consequent loss of catalytic activity. These ionic liquids were developed by Professor Luiz Longo's research group, with whom we established a partnership. Tests were also carried out with the substrates (R,S)1-(4-fluoro)phenylethylamine and (R,S)-1,2,3,4-tetrahydro 1-naphthylamine with the mentioned ionic liquids in order to expand the scope of the DKR methodology.
The main objective of this work is to study the methodology of Dynamic Kinetic Resolution (DKR) of primary amines using a palladium catalyst supported on dolomite, which was developed by the research group. DKR is a methodology used for the enantioselective synthesis from a racemic mixture. In this technique, two catalysts are used, one being enzymatic (Lipase Candida antarctica B - CaLB) which has a preference for the R enantiomer, and the other metallic which racemizes the unwanted enantiomer making it able to react again and generate the desired enantiomer in greater proportions. For the study, the class of amines was selected, as they are of great importance in the synthesis of various drugs and in the agrochemical industry. The metallic catalyst is palladium supported on dolomite, which showed good conversions and good enantiomeric excesses. In an attempt to improve this methodology, ionic liquids such as ammonium and phosphonium triflates (N4444.NTf2, P4444.NTf2, N8888.NTf2 and P8888.NTf2) were used, which can stabilize palladium nanoparticles, preventing their agglomeration and consequent loss of catalytic activity. These ionic liquids were developed by Professor Luiz Longo's research group, with whom we established a partnership. Tests were also carried out with the substrates (R,S)1-(4-fluoro)phenylethylamine and (R,S)-1,2,3,4-tetrahydro 1-naphthylamine with the mentioned ionic liquids in order to expand the scope of the DKR methodology.