Full text
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| Author(s): |
Leandro Piovan
Total Authors: 1
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| Document type: | Master's Dissertation |
| Press: | São Paulo. |
| Institution: | Universidade de São Paulo (USP). Conjunto das Químicas (IQ e FCF) (CQ/DBDCQ) |
| Defense date: | 2007-08-09 |
| Examining board members: |
André Luiz Meleiro Porto;
Massuo Jorge Kato;
Maria da Graça Nascimento
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| Advisor: | André Luiz Meleiro Porto |
| Abstract | |
In this work was considered the selectivity of reactions biocatalysted by basidiomycetes fungi with bifuncionalized compounds with ketone and selenide groups (1-2) or ketone and thio groups (3-4). The compounds 1-4 were prepared in according with methodologies from literature. During the synthesis of standard racemic β-hydroxyselenides 1a-4a and β-hydroxysulfides 3a-4a we noticed that chemical reduction using NaBH4 led to the preferential formation of the cis-(1a-4a) isomers. On the other hand, the bioreduction promoted by basidiomycetes fungi led to the preferential formation of trans-(1a-4a) isomers. Therefore, two complementary methodologies for preparation of β-hydroxyselenides and β-hydroxysulfides were established. Five strains of basidiomycetes fungi (Irpex lacteus CCB 196, Trametes rigida CCB 285, Pycnoporus sanguineus CCB 501, Trametes byssogenum CCB 203, Trametes versicolor CCB 202) were examined to aim at the preparation of β-hydroxyselenides and β-hydroxysulfides on the enantiomerically pure form. A qualitative study indicated that cells of T. rigida CCB 285 showed high selectivity led to the products cis-(1a-4a) and trans-(1a-4a) in high enantiomeric excess (ca 99 %). After that, a quantitative study allowed us to determine the isolated yields and the absolute configuration for the compounds cis-(1a-4a) and trans-(1a-4a). In the second part of this work was considered the application of Aspergillus terreus fungi in demethylation/dealkylation reactions by tertiary amines. The results indicated that those fungi showed a big potencial for demethylation reaction of aromatic tertiary amines. The reaction done on the pH = 7 led to the demethylated products with good values of conversion. Dealkylation reactions were not observed. (AU) | |