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2012 , Vol. 32 >Issue 07: 1284 - 1289

DOI: https://doi.org/10.6023/cjoc1112271

研究论文

氰化钠和醛及苦杏仁粗酶一锅法合成手性氰醇

  • 郑祖彪 ,
  • 姚璐璐 ,
  • 李忠洲 ,
  • 李新军 ,
  • 邹新琢
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  • 华东师范大学化学系 上海 200062

收稿日期: 2011-12-27

  修回日期: 2012-02-21

  网络出版日期: 2012-03-09

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Direct use of NaCN and aldehydes in one-pot asymmetric synthesis of cyanohydrins by crude (R)-oxynitrilase

  • Zheng Zubiao ,
  • Yao Lulu ,
  • Li Zhongzhou ,
  • Li Xinjun ,
  • Zou Xinzhuo
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  • Department of Chemistry, East China Normal University, Shanghai 200062

Received date: 2011-12-27

  Revised date: 2012-02-21

  Online published: 2012-03-09

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摘要

直接使用固体氰化钠代替易挥发的HCN 为氰源,用来源于苦杏仁的(R)-醇腈酶粗酶催化和醛的反应,并加入足量的HAc 来抑制非酶促反应和手性氰醇产物的外消旋化,一锅法合成了手性氰醇。考察了酸,(R)-醇腈酶粗酶,水,氰化钠和反应温度等因素对反应的影响。大部分反应底物的产物的产率及ee 值都大于95%。该方法简单,安全,低成本、高对映选择性和收率,具有很好的应用价值。

关键词： 氰化钠; (R)-醇腈酶; 一锅法; 不对称合成; 醛; 手性氰醇

本文引用格式

郑祖彪 , 姚璐璐 , 李忠洲 , 李新军 , 邹新琢 . 氰化钠和醛及苦杏仁粗酶一锅法合成手性氰醇[J]. 有机化学, 2012 , 32(07) : 1284 -1289 . DOI: 10.6023/cjoc1112271

Abstract

Solid sodium cyanide (NaCN) could be directly used to substitute volatile HCN as cyanide source in the one-pot asymmetric cyanohydrination of aldehydes catalyzed by crude (R)-oxynitrilase from almond with enough acetic acid to restrain the nonenzymatic reaction and racemization of chiral cyanohydrins. The effects of acid, crude (R)-oxynitrilase, volume ratio of water phase, NaCN and reaction temperature on the reaction were investigated. The yields and enantionmeric excess of most of products are higher than 95%. The proposed method has a high application value because of its simplicity, safety, and low cost as well as excellent enantioselectivities and yields.

Key words： NaCN; (R)-oxynitrilase; one-pot; asymmetric synthesis; aldehydes; cyanohydrin

参考文献

1. North, M.; Usanov, D. L.; Young, C. Chem. Rev. 2008, 108, 5146.  
2. Chen, P. R.;Yan, C.; Zhang, Y. Chin. J. Org. Chem. 2010, 30, 662(in Chinese).(陈沛然,颜超,张怡,有机化学,2010,30,662.)
3. Zheng, Z. B.; Li, X. J.; Wang, C. C., Zou, X. Z. Chin. J. Org. Chem. 2011, 31, 1624(in Chinese).(郑祖彪,李新军,王翠翠,邹新琢,有机化学,2011, 31, 1624.)
4. Breuer, M.; Ditrich, K. Habicher, T.; Hauer, B.; Kebeler, M.; Stürmer, R.; Zelinski, T. Angew. Chem., Int. Ed. 2004, 43, 788.  
5. Guo, S.; Huang, L. J.; Teng, D. W. Chemistry and Rioengineering, 2009, 26, 69(in Chinese).(郭帅,黄龙江,滕大为,化学与生物工程,2009, 26, 69.)
6. Effenberger, F.; Kremser, A.; Stelzer, U. Tetrahedron:Asymmetry, 1996, 7, 607.  
7. Nazabadioko, S.; Pérez, R. J.; Brieva, R.; Gotor, V. Tetrahedron:Asymmetry 1998, 9, 1597.  
8. Zheng, Z. B.; Wang, J.; Zhang, D. Y.; Guan, X. X.; Gao, S. X.; Chen, Z. Z.; Zou, X. Z. J. Agri. Food Chem. 2011, 59, 1171.  
9. Sakai, Y.; Mitote, J.; Matsumoto, K.; Katsuki, T. Chem. Commun. 2010, 46, 5787.  
10. Zhang, Z. P.; Wang, Z.; Zhang, R. Z.; Ding, K. L. Angew. Chem. Int. Ed. 2010, 49, 6746.  
11. Brovetto, M.; Gamenara, D.; Mendez, P. S.; Seoane, G. Chem. Rev. 2011, 111, 4346;
12. Gregory, R. J. H. Chem. Rev. 1999, 99, 3649.  
13. Cabirol, F. L.; Lim, A. E. C.; Hanefeld, U.; Sheldon, R. A. Org. Process Res. Dev. 2010, 14, 114.  
14. Bhunya, R.; Mahapatra, T.; Nanda, S. Tetrahedron: Asymmetry, 2009, 20, 1526.  
15. Rosenthaler, L. Biochem. Z. 1908, 14, 238.
16. Bhunya, R.; Jana, N.; Das, T.; Nanda, S. Synlett, 2009, 8, 1237.
17. Purkarthofer, T.; Skranc, W.; Schuster, C.; Griengl, H. Appl. Microbiol Biot. 2007, 76, 309.  
18. Griengl, H.; Hickel, A.; Johnson, D. V.; Kratky, C.; Schmidt, M.; Schwab, H. J. Chem. Soc.,Chem. Commun., 1997, 1933.
19. Effenberger, F. Angew. Chem. Int. Ed. Engl. 1994, 33, 1555.  
20. Zandbergen. P.; Van der Linden, J.; Brussee, J.; Van der Gen, A. Synthetic commun. 1991, 21, 1387.  
21. Becker, W.; Pfeil, E. J. Am. Chem. Soc. 1966, 88, 4299.  
22. Becker, W.; Freund, H.; Pfeil, E. Angew. Chem. Int. Ed. Engl., 1965, 4, 1079.
23. Effenberger, F.; Ziegler, T.; Forster, S. Angew. Chem. Int. Ed. Engl. 1987, 26, 458.  
24. Han, S. Q.; Lin, G. Q.; Li, Z. Y. Tetrahedron: Asymmetry, 1998, 9, 1835.  
25. Chen, P. R.; Han, S. Q.; Lin, G. Q.; Huang, H.; Li, Z. Y. Tetrahedron: Asymmetry, 2001, 12, 3273.  
26. Chen, P. R.; Han, S. Q.; Lin, G. Q.; Li, Z. Y. J. Org. Chem. 2002, 67, 8251.  
27. Ueatrongchit, T.; Tamura, K.; Ohmiya, T.; H-Kittikun, A.; Asano, Y. Enzyme Microb. Technol. 2010, 46, 456.  
28. Kiljunen, E.; Kanerva, L. T. Tetrahedron: Asymmetry, 1997, 8, 1225.  
29. Kiljunen, E.; Kanerva, L. T. Tetrahedron: Asymmetry, 1997, 8, 1551.  
30. Kiljunen, E.; Kanerva, L. T. Tetrahedron: Asymmetry, 1996, 7, 1105.  
31. GENG, X. H.; ZHOU, H.; Chen, P. R. Chin. J. Org. Chem. 2008, 28, 1157(in Chinese).(耿晓红,周辉,陈沛然,徐青,有机化学,2008, 28, 1157.)
32. Brussee, J.; Roos, E. C.; Van der Gen, A. Tetrahedron lett. 1988, 29, 4485.  
33. Xu, Q.; Xie, Y. L.; Geng, X. H.; Chen, P. R. Tetrahedron, 2010, 66, 624.  
34. Belokon, Y. N.; Blacker, A. J.; Clutterbuck, L. A.; Hogg, D.; North, M.; Reeve, C.; European Journal of Organic Chemistry, 2006, 20, 4609.
35. Schmidt, M.; Hevve, S.; Klempier, N.; Griengl, H. Tetrahedron, 1996, 52, 7833.  
36. Kumarswamy, G.; Ankamma, K. Org. Prep. Proced. Int. 2008, 40, 447.  
37. Inagaki, M.; Hiratake, J.; Nishioka, T.; Oda, J. J. Org. Chem. 1992, 57, 5643.  
38. Sakai, T.; Wang, K.; Ema, T. Tetrahedron, 2008, 64, 2178.  
39. Ohta, H.; Hiraga, S.; Miyamoto, K.; Tsuchihashi, G. Agric. Biol. Chem. 1988, 52, 3023.  
40. Lin, G. Q.; Han, S. Q.; Li, Z. Y. Tetrahedron, 1999, 55, 3531.  
41. Liu, S. L.; Zong, M. H.; Tu, R.; Zhou, F. Prog. Biochem. Biophys. 2001, 28, 542(in Chinese).(刘森林,宗敏华,涂然,周番,生物化学与生物物理进展,2001, 28, 542.)
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