Sequential deracemization of sulfoxides via whole-cell resolution and heterogeneous oxidation

A new concept for the synthesis of asymmetric sulfoxides exploiting sequential deracemization of racemic (rac) sulfoxides using a two-stage protocol had been developed. Enantio-pure sulfoxide was obtained using Escherichia coli (E. coli) cells to catalyze the reduction of (R)-sulfoxide to the thioether, and then using a heterogeneous Ta2O5–SiO2 catalyst for catalyzing the oxidation of the ethers to the rac-sulfoxide. The performance of E. coli depended on the strain and the conditions under which the bacteria growth was carried out (e.g. source of carbon, presence of vitamins, and concentration of dimethyl sulfoxide, DMSO). Under optimized conditions, the E. coli cells performed the rac-sulfoxide resolution for different sufoxides leading to the best enantiomeric excess (ee) of around 62% (S)-MTSO (methyl tolyl sulfoxide) with 49% conversion of the rac-MTSO. The sequential deracemization process applied for rac-MTSO was cyclically performed leading to 97.5% ee of (S)-sulfoxide and a 56% yield in (S)-sulfoxide after three deracemization cycles of rac-MTSO.

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► Enantioreduction of rac-sulfoxide was performed using Escherichia coli biocatalyst.
► Optimum growth conditions of E. coli biocatalyst have been set up.
► Selectivity of the biocatalyst was tested for different rac-sulfoxides.
► Sequential two-step deracemization was performed for rac-sulfoxides.