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Asymmetry Synthesis of Chiral Sulfoxide Catalyzed by Chloroperoxidase

  • Wang Limin ,
  • Wu Jinyue ,
  • Jiang Yucheng ,
  • Hu Mancheng ,
  • Li Shuni ,
  • Zhai Quanguo
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  • 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 date: 2011-06-21

  Revised date: 2011-09-02

  Online 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).

Abstract

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.

Cite this article

Wang Limin , Wu Jinyue , Jiang Yucheng , Hu Mancheng , Li Shuni , Zhai Quanguo . Asymmetry Synthesis of Chiral Sulfoxide Catalyzed by Chloroperoxidase[J]. Acta Chimica Sinica, 2012 , 0(04) : 465 -470 . DOI: 10.6023/A1106212

References

1 Fernández, I.; Khiar, N. Chem. Rev. 2003, 103, 3651.  

2 Li, L.; Shi, J. Adv. Synth. Catal. 2005, 347, 1745.  

3 Jacobsen, E. N.; Paltz, A.; Yamamoto, H. Comprehensive Asymmetric Catalysis I-III, Springer, Heidelberg, 1999, p. 1178.  

4 Li, S. K.; Bai, D. L. Prog. Chem. 2001, 13, 351 (in Chinese). (李树坤, 白东鲁, 化学进展, 2001, 13, 351.)

5 Kobayashi, S.; Ogawa, C.; Konihi, H.; Suqiura, M. J. Am. Chem. Soc. 2003, 125, 6610.  

6 Bolm, C.; Simic, O. J. Am. Chem. Soc. 2001, 123, 3830.  

7 Andersson, M. A.; Allenmark, S. G. Tetrahedron 1998, 54, 15293.  

8 Holland, H. L.; Brown, F. M.; Larsem, B. G. Tetrahedron: Asymmetry 1995, 6, 1561.  

9 Pitchen, P.; Du?ach, E.; Deshmukh, M. N.; Kagan, H. B. J. Am. Chem. Soc. 1984, 106, 8188.  

10 Brink, H. B.; Holland, H. L.; Schoemaker, H. E.; Lingen, H.; Wever, R. Tetrahedron: Asymmetry 1999, 10, 4563.  

11 Pasta, P.; Carrea, G.; Holland, H. L.; Dallavalle, S. Tetrahedron: Asymmetry 1995, 6, 933.  

12 Morris, D. R.; Hager, L. P. J. Biol. Chem. 1966, 241, 1763.

13 Hager, L. P.; Morris, D. R.; Brown, F. S.; Eberwein, H. J. Biol. Chem. 1966, 241, 1769.

14 Park, J. B.; Clark, D. S. Biotechnol. Bioeng. 2006, 93, 1190.  

15 Ayala, M.; Batista, C. V.; Vazquez-Duhalt, R. J. Biol. Inorg. Chem. 2011, 16, 63.  

16 Chang, C. S.; Yamazaki, I.; Sinclairp, R.; Khalid, S.; Powers, L. Biochemistry 1993, 32, 923.  

17 Sundaramoorthy, M.; Terner, J.; Poulos, T. L. Structure 1995, 3, 1367.  

18 Egawa, T.; Proshlyskov, D. A.; Miki, H.; Makino, R.; Ogura, T.; Kitagawa, T.; Ishimura, Y. J. Biol. Inorg. Chem. 2001, 6, 46.  

19 Jiang, T. J.; Ji, X. S.; Yuan, Z. Y. Acta Biochim. Biophys. Sin. 1998, 30, 132 (in Chinese). (蒋太交, 吉鑫松, 袁中一, 生物化学与生物物理学报, 1998, 30, 132.)

20 Rantwijk, F.; Sheldon, R. A. Curr. Opin. Biotechnol. 2000, 11, 554.  
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