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| Author(s): |
Rodrigo dos Santos Martins
Total Authors: 1
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| Document type: | Master's Dissertation |
| Press: | Campinas, SP. |
| Institution: | Universidade Estadual de Campinas (UNICAMP). Instituto de Química |
| Defense date: | 2009-11-30 |
| Examining board members: |
Paulo José Samenho Moran;
Maria da Graça Nascimento;
Anita Jocelyne Marsaioli
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| Advisor: | Paulo José Samenho Moran |
| Abstract | |
Recently, the racemate 2-(4-chlorophenylthio)-1-(3,4-dimethoxyphenyl)-1- propanone (15b) that is an analog synthetic of neolignans, isolated from Virola surinamensis shows anti-leismania activity. In this work, we performed the bioreduction of 1-(3,4-dimethoxy)1,2-propanodione (1c) mediated by baker yeast (Saccharomyces cerevisiae) affording (2S)-2-hydroxy-1-(3,4-dimethoxyphenyl)-1-propanone (2c) in 60% yield and 93% e.e. which is an intermediate for 15b. Consecutively, protocols were applied to perform SN2 reaction of 2c and p-chlorotiophenol in order to synthesize optically pure 15b. The reaction of sulfonic ester of (+)-(2S)-2c with p-chlorotiophenol catalyzed by phase transfer catalysis (PTC) shows to be a better strategy to obtain 15b. Both enantiomers of 15b were synthesized, (-)-15b was obtained in 10% yield and >95% e.e. from sulfonic ester from 2c, and (+)-15b was obtained in 90% yield and 60% e.e. from (-)-2-chloro-1- (3,4-dimethoxyphenyl)-1-propanone that was a by-product formed in the synthesis of sulfonic ester from 2c. In addition, an alternative methodology for obtaining 2-hydroxy-1-aryl-1-propanone (2) was applied through kinetic resolution of 1-phenylpropane-1,2-propanediol by biocatalytic oxidation mediated by bakers yeast. After optimization of this process, the (2S)-2-hydroxy-1-phenyl-1-propanone (2a) and (1S,2R)-4a were obtained in 25% yield and 83% e.e. and 30% yield and 68% e.e. respectively from (±)-anti-1-phenyl-1,2-propanediol (anti-4a) after 7 days. The same protocol was applied with other microorganisms as Geotrichum candidum that produced (1S,2R)-4a in 30% yield and 99% e.e. after 5 days. (AU) | |