51. The selective oxidation of thioanisole to sulfoxide using a highly efficient electroenzymatic cascade system.
- Author
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Zhu, Xuefang, Liu, Xiyue, Ding, Yu, Li, Shuni, Jiang, Yucheng, and Chen, Yu
- Subjects
SULFOXIDES ,ANISOLE ,DIMETHYL sulfoxide ,POLYETHYLENEIMINE ,ENZYME stability ,OXIDATION ,DIMETHYL sulfone ,ASYMMETRIC synthesis - Abstract
Sulfoxides are remarkably useful in asymmetric synthesis and drug development. Herein, we propose a new electroenzymatic cascade route to selectively synthesize methyl phenyl sulfoxide rather than methyl phenyl sulfone by the oxidation of thioanisole. Chloroperoxidase (CPO) functionalized with 1-ethyl-3-methylimidazolium bromide (IL
EMB ) is encapsulated into dendritic N-doped mesoporous carbon nanospheres (NMCNs) modified with polyethyleneimine (NMCNs-PEI) to form a biohybrid (CPO-ILEMB @NMCNs-PEI). The in situ generation of hydrogen peroxide (H2 O2 ) species by the two-electron oxygen reduction reaction (2e− ORR) on NMCNs-PEI initiates the subsequent selective oxidation of thioanisole by CPO-ILEMB . NMCNs-PEI shows not only high electroactivity for the 2e− ORR but also good biocompatibility for CPO-ILEMB immobilization. The mesopores in NMCNs-PEI can provide a protective space for the encapsulated enzyme, ensuring the operational stability of the enzyme and avoiding the escape of H2 O2 , which result in high catalytic activity. The experimental results suggest that the catalytic efficiency of the electroenzymatic cascade system with the CPO-ILEMB @NMCNs-PEI biohybrid is up to 4.5 times higher than that of the free CPO-ILEMB catalytic system with H2 O2 generated by NMCNs-PEI for the oxidation of thioanisole to produce methyl phenyl sulfoxide. [ABSTRACT FROM AUTHOR]- Published
- 2024
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