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Doctoral Thesis
DOI
10.11606/T.46.2005.tde-17102007-164616
Document
Author
Full name
Giuliano Cesar Clososki
E-mail
Institute/School/College
Knowledge Area
Date of Defense
Published
São Paulo, 2005
Supervisor
Committee
Comasseto, João Valdir (President)
Andrade, Leandro Helgueira de
Marzorati, Liliana
Moran, Paulo José Samenho
Simonelli, Fábio
Title in Portuguese
Aplicação da biocatálise na síntese de γ-butirolactonas bioativas quirais: novos reagentes visando a preparação estereosseletiva de análogos da vitamina A
Keywords in Portuguese
Biocatálise
Butirolactonas
Vitamina A
Abstract in Portuguese
O primeiro capítulo desta tese é dedicado aos estudos que visaram à aplicação da biocatálise na síntese de γ-butirolactonas quirais. Inicialmente investigou-se a preparação de fenilseleno-γ-butirolactonas quirais, através da resolução cinética enzimática dos fenilseleno-γ-hidróxi ésteres correspondentes. Através desta estratégia, ambos os enantiômeros da fenilseleno-γ-butirolactona foram preparados em excessos enantioméricos razoáveis. Ainda no primeiro capítulo é demonstrado o potencial sintético do (R)-3-(5-oxotetraidro-2-furanil)-propanoato de benzila, obtido através de uma enantiolactonização catalisada por PPL na etapa chave. Este intermediário quiral foi utilizado com sucesso na síntese enantiosseletiva da (R)- e da (S)-y-jasmolactona, aromatizantes de interesse industrial, além de ambos enantiômeros da (7Z)-7,15-hexadecadien-4-oIida, feromônio sexual da "Yellowish Elongate Chafer, Heptophy/a picea" . A segunda parte deste trabalho foi efetuada na Universidade da Califórnia, EUA, sob a orientação do professor Bruce H. Lipshutz, durante o período de novembro de 2003 a outubro de 2004. Dois novos reagentes foram desenvolvidos e aplicados com sucesso na preparação estereosseletiva de polienos conjugados com estrutura análoga a da vitamina A .
Title in English
Application of biocatalysis in the enantioselective synthesis of chiral gamma-butyrolactones: new reagents for the stereoselective preparation of analogous of vitamin A
Keywords in English
Biocatalysis
Butyrolactones
Vitamin A
Abstract in English
The first chapter of this thesis is dedicated to the studies on the application of biocatalysis in the synthesis of chiral γ-butyrolactones. We started investigating the preparation of phenylselanyl-γ-butyrolactones through the kinetic enzymatic resolution of the corresponding phenylselanyl-γ-hydroxyesters. By using this strategy both enantiomers of phenylselanyl-γ-butyrolactone were prepared in reasonable enantiomeric excesses . In the first chapter is also demonstrated the synthetic potential of benzyl 3[(R)-tetrahydro-5-oxofuran-2-yl] propanoate, obtained through a PPL catalyzed enantiolactonization in the key step. This chiral intermediate was successfully applied in the enantioselective synthesis of (R)- and (S)-γ-jasmolactone, flavors that find industrial use, and both enantiomers of (7Z)-7,15-hexadecadien-4-olide, the sex pheromone of Yellowish Elongate Chafer, Heptophy/a picea. The second part of this work was carried out at University of California, USA, between November 2003 and October 2004, under supervision of Professor Bruce H. Lipshutz. Two new reagents were developed and successfully applied in the stereoselective synthesis of conjugated polienes analogs to vitamin A .
 
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Publishing Date
2007-10-23
 
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