RESUMO
Enantiopure ß-hydroxy sulfoxides and catechol sulfoxides were obtained, by chemoenzymatic synthesis, involving dioxygenase-catalysed benzylic hydroxylation or arene cis-dihydroxylation and cis-diol dehydrogenase-catalysed dehydrogenation. Absolute configurations of chiral hydroxy sulfoxides were determined by X-ray crystallography, ECD spectroscopy and stereochemical correlation. The application of a new range of ß-hydroxy sulfoxides as chiral ligands was examined.
Assuntos
Dioxigenases/metabolismo , Sulfóxidos/química , Sulfóxidos/metabolismo , Biocatálise , Cristalografia por Raios X , Hidroxilação , Ligantes , Modelos Moleculares , Estrutura Molecular , Sulfóxidos/síntese químicaRESUMO
Direct and indirect evidence, of unexpected stereoselective reductase-catalysed deoxygenations of sulfoxides, was found. The deoxygenations proceeded simultaneously, with the expected dioxygenase-catalysed asymmetric sulfoxidation of sulfides, during some biotransformations with the aerobic bacterium Pseudomonas putida UV4. Stereoselective reductase-catalysed asymmetric deoxygenation of racemic alkylaryl, dialkyl and phenolic sulfoxides was observed, without evidence of the reverse sulfoxidation reaction, using anaerobic bacterial strains. A purified dimethyl sulfoxide reductase, obtained from the intact cells of the anaerobic bacterium Citrobacter braakii DMSO 11, yielded, from the corresponding racemates, enantiopure alkylaryl sulfoxide and thiosulfinate samples.
Assuntos
Biocatálise , Citrobacter/enzimologia , Oxirredutases/metabolismo , Pseudomonas putida/enzimologia , Safrol/análogos & derivados , Aerobiose , Anaerobiose , Estrutura Molecular , Oxirredução , Safrol/química , Safrol/metabolismo , Estereoisomerismo , Especificidade por SubstratoRESUMO
Dioxygenase-catalysed trioxygenation of alkyl phenyl sulfides and alkyl benzenes yields enantiopure cis-dihydrodiol sulfoxides and triols respectively; naphthalene cis-dihydrodiol dehydrogenase-catalysed aromatisation of these diastereoisomers gives enantiopure catechols of either configuration.
Assuntos
Benzeno/metabolismo , Catecóis/química , Catecóis/metabolismo , Oxirredutases/metabolismo , Oxigenases/metabolismo , Sulfetos/metabolismo , Benzeno/química , Catálise , Isomerismo , Oxirredução , Sulfetos/químicaRESUMO
Enantioenriched thiosulfinates have been obtained by dioxygenase- and chloroperoxidase-catalysed oxidation of 1,2-disulfides and dimethyl sulfoxide reductase-catalysed deoxygenation.
