Acta Chimica Sinica ›› 2012, Vol. 0 ›› Issue (04): 465-470.DOI: 10.6023/A1106212 Previous Articles     Next Articles

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汪丽敏a, 吴金跃a, 蒋育澄a,b, 胡满成a,b, 李淑妮a,b, 翟全国a,b   

  1. a 陕西师范大学化学化工学院 西安 710062;
    b 陕西师范大学大分子科学陕西省重点实验室 西安 710062
  • 投稿日期:2011-06-21 修回日期:2011-09-02 发布日期:2011-10-20
  • 通讯作者: 蒋育澄
  • 基金资助:

    国家自然科学基金(No. 20876094)及中央高校基本科研业务费专项资金(No. GK201001005)资助.

Asymmetry Synthesis of Chiral Sulfoxide Catalyzed by Chloroperoxidase

Wang Limina, Wu Jinyuea, Jiang Yuchenga,b, Hu Manchenga,b, Li Shunia,b, Zhai Quanguoa,b   

  1. a School of Chemistry & Chemical Engineering, Shaanxi Normal University, Xi'an 710062;
    b Key Laboratory of Macromolecular Science of Shaanxi Province, Shaanxi Normal University, Xi'an 710062
  • Received:2011-06-21 Revised:2011-09-02 Published:2011-10-20
  • Supported by:

    This work was supported by the National Natural Science Foundation of China (No. 20876094) and the Fundamental Research Funds for the Central Universities (No. GK201001005).

Benzyl alkyl sulfide was turned into chiral R-sulfoxide using chloroperoxidase (CPO)-catalyzed oxidation of (TBHP) based on CPO’s chiral recognization to organic substrate. The yield of aim products was enhanced by the introduction of polyhydroxy compound and quaternary ammonium salt. The reaction was mainly controlled by factors such as pH, oxidants, reaction time, molar ratio of oxidant/substrate, and CPO consumption. The sulfoxide yield and enantiomeric excess (ee) reached 65.5% and 96.3% when polyhydroxy compounds (glycerol, PEG400 or PEG600) were introduced into reaction system. The yield and ee of 78.2%~68.5% and 95.4%~94% were obtained when quaternary ammonium salt (TEABr, TPABr or TBABr) was introduced. UV-vis and fluorescence spectrum assay indicated that it was easier for CPO to bind with the substrate because the introduction of above additives would intensify the exposure of heme. Moreover, it was also favorable for CPO catalytic performance due to the improvement of α-helix structure of CPO. Compared to those reported methods, the preparation of chiral sulfoxide catalyzed by CPO was very efficient. CPO consumption was very small which would ensure its potential application in industry.

Key words: chloroperoxidase, chiral sulfoxide, enantio-sulfoxidation, polyhydroxy compound, quaternary ammonium salt