Asymmetric Synthesis of an (R)-Cyanohydrin Using Enzymes Entrapped in Lens-Shaped Gels

Organic Letters

Volumn 3, Issue 13, 2001, Pages 1967-1971

  Gröger, Harald ^a   Capan, Emine ^b   Barthuber, Anita ^a   Vorlop, Klaus Dieter ^b  

^a EVONIK INDUSTRIES AG   (Germany)

^b INSTITUTE FOR EPIDEMIOLOGY AND PATHOGEN DIAGNOSTICS   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0042839682     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol015920g     Document Type: Article

References (33)

1. Important industrial applications of chiral cyanohydrins are the manufacture of pyrethroids (insecticides), e.g., deltamethrin, as well as the production of α-hydroxy carboxylic acids as intermediates for pharmaceuticals and resolving agents. For example, (R)-mandelic acid (a derivative of (R)-mandelonitrile) represents a fine chemical which is produced on multihundred ton scale.
2. For excellent reviews about the asymmetric synthesis of cyanohydrins, see: (a) Effenberger, F. Angew. Chem. 1994, 106, 1609-1619; Angew. Chem., Int. Ed. Engl. 1994, 33, 1555-1564.
3. For excellent reviews about the asymmetric synthesis of cyanohydrins, see: (a) Effenberger, F. Angew. Chem. 1994, 106, 1609-1619; Angew. Chem., Int. Ed. Engl. 1994, 33, 1555-1564.
4. (b) Gregory, R. J. H. Chem. Rev. 1999, 99, 3649-3682.
5. (a) Hamashima, Y.; Sawada, D.; Kanai, M.; Shibasaki, M. J. Am. Chem. Soc. 1999, 121, 2641-2642.
6. (b) Sawada, D.; Shibasaki, M. Angew. Chem. 2000, 112, 215-218; Angew. Chem., Int. Ed. 2000, 39, 209-213.
7. (b) Sawada, D.; Shibasaki, M. Angew. Chem. 2000, 112, 215-218; Angew. Chem., Int. Ed. 2000, 39, 209-213.
8. (c) Kanai, M.; Hamashima, Y.; Shibasaki, M. Tetrahedron Lett. 2000, 41. 2405-2409.
9. (d) Hamashima, Y.; Kanai, M.; Shibasaki, M. J. Am. Chem. Soc. 2000, 122, 7412-7413.
10. (e) Hamashima, Y.; Kanai, M.; Shibasaki, M. Tetrahedron Lett. 2001, 42, 691-694.
11. (f) Tanaka, K.; Mori, A.; Inoue, S. J. Org. Chem. 1990, 55, 181-185.
12. (g) Mori, A.; Nitta, H.; Kudo, M.; Inoue, S.; Tetrahedron Lett. 1991, 32, 4333-4336.
13. (h) For reviews, see ref 2.
14. (a) Effenberger, F.; Ziegler, T.; Förster, S. Angew. Chem. 1987, 99, 491-492; Angew. Chem., Int. Ed. Engl. 1987, 26, 458-460.
15. (a) Effenberger, F.; Ziegler, T.; Förster, S. Angew. Chem. 1987, 99, 491-492; Angew. Chem., Int. Ed. Engl. 1987, 26, 458-460.
16. (b) Wehtje, E.; Adlercreutz, P.; Mattiasson, B. Biotechnol. Bioeng. 1990, 36, 39-46.
17. (c) Wehtje, E.; Adlercreutz, P.; Mattiasson, B. Biotechnol. Bioeng. 1993, 41, 171-178.
18. (d) Gill, I.; Ballesteros, A. J. Am. Chem. Soc. 1999, 120, 8587-8598.
19. (e) At pH 5.5, a low ee of 77% was obtained.
20. One of the rare exceptions of a very practical immobilization method represents the production of (R)-mandelonitrile with the continuous membrane reactor technique which is mainly applied for continuous processes, see: (a) Vasic-Racki, D.; Jonas, M.; Wandrey, C., Hummel W.; Kula, M.-R. Appl. Microbiol. Biotechnol. 1989, 31, 215-222.
21. (b) Bommarius, A. S.; Drauz, K.; Groeger, U.; Wandrey, C. In Chirality in Industry; Collins, A. N., Sheldrake, G. N., Crosby, J., Eds.; John Wiley & Sons Ltd: New York, 1992; Chapter 20, pp 371-397.
22. (a) Despite the high potential of immobilized biocatalysts, in a United Nations publication from 1989, only eight industrial processes have been reported which are based on immobilized enzymes or microbial cells see: Klyosov Report, A. A. UNIDO/IPTC. 93, V-89-61316. Order No. PB90-210360, 111 pp.
23. (b) The manufacture of 7-aminocephalosporanic acid represents (probably) the most important industrial process which is based on the use of an immobilized enzyme.
24. (a) Jekel, M.; Buhr, A.; Willke, T.; Vorlop, K.-D. Chem. Eng. Technol. 1998, 21, 275-278.
25. (b) Wittlich, P.; Schlieker, M.; Jahnz, U.; Willke, T.; Vorlop, K.-D. Proc. 9th Eur. Congr. Biotechnol. 1999, No. P2762, ISBN 805215-1-5.
26. (c) Welter, K.; Willke, T.; Vorlop, K.-D. SchrR Nachwachsende Rohstoffe 1999, 14, 520-521.
27. (d) Wittlich P., Schlieker, M., Lutz, J.; Reimann, C.; Willke, T.; Vorlop, K.-D. SchrR Nachwachsende Rohstoffe 1999, 14, 524-532.
28. (e) Durieux, A.; Nicolay, X.; Simon, J.-P. Biotechnol. Lett. 2000, 22, 1679-1684.
29. For information about commercial applications of this type of immobilization technology as well as commercial products from geniaLab, see: http://www.geniaLab.de.
30. The experiments described herein have been earned out using a nonpurified oxynitrilase purchased from ASA Spezialenzyme GmbH, Braunschweig (specific activity, 13.6 U/mg proteine; amount of proteine, 7.6 ng/mL). Although purity and activity are somewhat lower compared with those of other commercially available, highly purified oxynitrilases, this enzyme was chosen on basis of cost.
31. The physical properties of such type of lens-shaped hydrogels in general have been described earlier; for details, see ref 7.
32. The reaction conditions for the preparation of the lens-shaped hydrogels can be varied widely, e.g., resulting in a different catalyst loading.
33. In general, the catalytic activity of oxynitrilases is determined via this cleavage reaction of mandelonitrile (dehydrocyanation reaction). The reaction course has been determined according of the increase of the concentration of benzaldehyde (extinction E) which has been detected with a photometer (at 250 nm). For further details, see Supporting Information.