Magnetic nanoparticles (MNPs) with a core diameter of 30 nm comprising several iron oxide crystals, a poly(glycidyl methacrylate) (PGMA) shell with a thickness of 30 nm, and a surface coated with chloroperoxidase (CPO) were facilely fabricated as a nanobiocatalyst for asymmetric sulfoxidation. The covalently bound CPO did not change the original conformation of the active site and showed the same catalytic activity and enantioselectivity as free CPO for the sulfoxidation of thioanisole to produce (R)-methyl phenyl sulfoxide in >99% ee. The thick PGMA shell significantly increased the stability of the nanobiocatalyst: no loss of the sulfoxidation activity was observed after 11 times of recycling and reuse of the catalyst. Thus, the nanobiocatalyst fabricated here showed the best performance among nanosized biocatalyst particles regarding both the retaining of free enzyme activity and the recycling of catalyst. This is also the first example of a nanobiocatalyst for asymmetric oxidation, and the concept could be generally applicable for fabricating active and recyclable nanobiocatalysts.

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Cascade biocatalysis via intracellular epoxidation and hydrolysis was developed as a green and efficient method for enantioselective dihydroxylation of aryl olefins to prepare chiral vicinal diols in high ee and high yield. Escherichia coli (SSP1) coexpressing styrene monooxygenase (SMO) and epoxide hydrolase SpEH was developed as a simple and efficient biocatalyst for S-enantioselective dihydroxylation of terminal aryl olefins 1a−15a to give (S)-vicinal diols 1c−15c in high ee (97.5−98.6% for 10 diols; 92.2−93.9% for 3 diols) and high yield (91−99% for 6 diols; 86−88% for 2 diols; 67% for 3 diols). Combining SMO and epoxide hydrolase StEH showing complementary regioselectivity to SpEH as a biocatalyst for the cascade biocatalysis gave rise to R-enantioselective dihydroxylation of aryl olefins, being the first example of this kind of reversing the overall enantioselectivity of cascade biocatalysis. E. coli (SST1) coexpressing SMO and StEH was also engineered as a green and efficient biocatalyst for R-dihydroxylation of terminal aryl olefins 1a−15a to give (R)-vicinal diols 1c−15c in high ee (94.2−98.2% for 7 diols; 84.2−89.9% for 6 diols) and high yield (90−99% for 6 diols; 85−89% for 5 diols; 65% for 1 diol). E. coli (SSP1) and E. coli (SST1) catalyzed the trans-dihydroxylation of trans-aryl olefin 16a and cis-aryl olefin 17a with excellent and complementary stereoselectivity, giving each of the four stereoisomers of 1-phenyl-1,2-propanediol 16c in high ee and de, respectively. Both strains catalyzed the trans-dihydroxylation of aryl cyclic olefins 18a and 19a to afford the same trans-cyclic diols (1R,2R)-18c and (1R,2R)-19c, respectively, in excellent ee and de. This type of cascade biocatalysis provides a tool that is complementary to Sharpless dihydroxylation, accepting cis-alkene and offering enantioselective trans-dihydroxylation.