Lipase-catalysed enantioselective hydrolysis of bicyclo[3.2.0]heptanol esters in supercritical carbon dioxide

Bioorganic and Medicinal Chemistry Letters

Volumn 7, Issue 7, 1997, Pages 811-816

  Parve, Omar ^a   Vallikivi, Imre ^a   Lahe, Lilja ^a   Metsala, Andrus ^a   Lille, Ülo ^a   Tõugu, Vello ^b   Vija, Heiki ^b   Pehk, Tõnis ^b  

^a TALLINN UNIVERSITY OF TECHNOLOGY   (Estonia)

^b NATIONAL INSTITUTE OF CHEMICAL PHYSICS AND BIOPHYSICS   (Estonia)

Author keywords

[No Author keywords available]

Indexed keywords

BICYCLO[3.2.0]HEPTANE DERIVATIVE; TRIACYLGLYCEROL LIPASE;

ARTICLE; DRUG PURIFICATION; DRUG SYNTHESIS; ENANTIOMER; ENZYME ACTIVITY; HYDROLYSIS; OPTICAL RESOLUTION; TECHNIQUE;

EID: 0030907423     PISSN: 0960894X     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0960-894X(97)00103-0     Document Type: Article

References (33)

1. Hammond, D.A.; Karel, M.; Klibanov, A.M. Appl. Biochem. Biotech., 1985, 11, 393-400. Nakamura, K.; Chi, J.M.; Jamada, J.; Jano, T. Chem. Eng. Commun., 1985, 45, 207-212. Randolph, T.W.; Blanch, H.W.; Prausnitz, J.M; Wilke, C.R. Biotechnol. Lett., 1985, 7, 325-328.
2. Hammond, D.A.; Karel, M.; Klibanov, A.M. Appl. Biochem. Biotech., 1985, 11, 393-400. Nakamura, K.; Chi, J.M.; Jamada, J.; Jano, T. Chem. Eng. Commun., 1985, 45, 207-212. Randolph, T.W.; Blanch, H.W.; Prausnitz, J.M; Wilke, C.R. Biotechnol. Lett., 1985, 7, 325-328.
3. Hammond, D.A.; Karel, M.; Klibanov, A.M. Appl. Biochem. Biotech., 1985, 11, 393-400. Nakamura, K.; Chi, J.M.; Jamada, J.; Jano, T. Chem. Eng. Commun., 1985, 45, 207-212. Randolph, T.W.; Blanch, H.W.; Prausnitz, J.M; Wilke, C.R. Biotechnol. Lett., 1985, 7, 325-328.
4. Perrut, M. High Pressure and Biotechnology. Balny, C.; Hayashi, R.; Heremans, K. and Masson, P., Eds. Colloque INSERM/John Libbey Eurotext., 1992, 224, 401-410.
5. Kamat, S.; Critchley, G.; Beckman, E.J.; Russell, A.J. Biotechnol. Bioeng., 1995, 46, 610-620.
6. Michor, H.; Marr, R.; Gamse, T.; Schilling, T.; Klingsbichel, E.; Schwab, H. Biotechnol. Lett., 1996, 18, 79-84.
7. Kamat, S.V.; Iwaskewycz, B.; Beckman, E.J.; Russell, A.J. Proc. Natl. Acad. Sci. USA, 1993, 90, 2940-2944.
8. Dumont, T.; Barth, D.; Perrut, M. J. Supercrit. Fluids, 1993, 6, 85-89.
9. Knez, Z.; Rizner, V.; Habulin, M.; Bauman, D. J. Am. Oil Chem. Soc., 1995, 72, 1345-1349.
10. Martins, J.F.; Borges de Carvalho, I.; Corrêa de Sampaio, T.; Barreiros, S. Enzyme Microb. Technol., 1994, 16, 785-790.
11. Chen, Sh.T.; Tsai, Ch.-F.; Wang, K.-Ts. Bioorg. Medicinal Chem. Lett., 1994, 4, 625-630.
12. Santaniello, E.; Ferraboschi, P.; Grisenti, P.; Manzocchi, A. Chem. Rev., 1992, 92, 1071-1140.
13. Theil, F. Chem. Rev., 1995, 95, 2203-2227.
14. Faber, K. Biotransformations in Organic Chemistry - A Textbook. Springer-Verlag, 1995, pp. 80-105.
15. Khmelnitsky, Y.L.; Welch, S.H.; Clark, D.S.; Dordick, J.S. J. Am. Chem. Soc., 1994, 116, 2647-2648.
16. Newton, R.F. New Synthetic Routes to Prostaglandins and Thromboxanes, Roberts, S.M. and Scheinmann, F., Ed-s; Academic Press: London, 1982, pp.61-104.
17. Cotterill, I.C.; Macfarlane, E.L.A.; Roberts, S.M. J. Chem. Soc. Perkin Trans.I, 1988, 3387-3389.
18. Klempier, N.; Geymayer, P.; Stadler, P.; Faber, K.; Griengl, H. Tetrahedron: Asymmetry, 1990, 1, 111-118.
19. Cotterill, I.C.; Sutherland, A.S.; Roberts, S.M.; Grobbauer, R.; Spreitz, J.; Faber, K. J. Chem. Soc. Perkin Trans. I, 1991, 1365-1368.
20. Parve, O.; Pals, A.; Kadarpik, V.; Lahe, L.; Lille, Ü.; Sikk, P.; Lõokene, A., Välimäe. T. Bioorg. Medicinal Chem. Lett., 1993, 3, 359-362.
21. The initial rates of Lipolase-catalysed hydrolysis (μmol/min per 1.0 ml of Lipolase) in water of the substrates (1)-(6) were recorded on a pH-stat: (1) - 0, (2) - 1.36, (3) - 0.85, (4) - 0.42, (5) - very slow, (6) - 0. Details will be available in: "Lipase-Catalysed Enantioselective Hydrolysis: Interpretation of the Kinetic Results in Terms of Frontier Orbital Localisation" by O. Parve et al. Tetrahedron (in press).
22. 6/EtOAc 10/1).
23. Greene, T.W.; Wuts, P.G.M. Protective Groups in Org. Synthesis, 2nd Ed., John Wiley & Sons Inc., pp. 178-197.
24. The substrate (3) was prepared following the scheme: Formula Represented.
25. Newton, R.F.; Paton, J.; Reynolds, D.P.; Young, S.; Roberts, S.M. J.C.S. Chem. Comm., 1979, 908-909.
26. 26 preparation. The reactor was placed in a thermostat with t°=39-40°C. Liquid carbon dioxide was pumped into the reaction vessel by a Chromatographic piston pump with cooled pumpheads (DuPont Instruments) until the pressure reached the desired value (200 bar). After the reaction time was over the samples were collected into methanol through a flow resistor. The samples were evaporated, separated over silica and analyzed. Acetone washings of the reactor system were not further investigated.
27. 6)) (9) was obtained also supporting the conclusion that equilibrium was reached at 7-10% conversion under the conditions used.
28. Humicola lanuginosa lipase preparation Lipolase 100T was kindly provided by Novo Nordisk.
29. 2-tank; 2 - high pressure pump; 3 and 5 - pressure gauge; 4 and 7 - HPLC valve; 6 - reactor; 8 - resistor; 9 -sample collection; 10 - thermostat.
30. 2 medium. See: Dumont, T., Barth, D.; Corbier, C.; Branlant, G.; Perrut, M. Biotechnol. Bioeng., 1992, 39, 329-333.
31. The hydroxyesters (2) and (3) were hydrolysed readily to conv 35-40% at p=170 bar (other conditions were kept constant), while ketoester (4) was hydrolysed to conv. 2-3% under such pressure.
32. 2 of the substrates (1)-(6) were calculated: (1) E=45, (2) E=8, (3) E=30, (4) E=40, (5) E=25; (6) E=18. The calculations were based on the e.e. of the reaction products (Table) as well as conversion rates 40% and 3% estimated for the substrates (1)-(3) and (4)-(6), respectively. These conversion rates have been estimated roughly by amounts as well as by e.e. of the starting material recovered. Moreover, the E values obtained correspond to the systems in equilibrium being therefore assumed probably to change during the process as well as to differ from those corresponding to the irreversible hydrolysis. Thus, in our opinion enantioselectivity has to be reinvestigated along with the optimisation of the process.
33. 3. n-Hexane was found to be a worse medium giving a less clean product. Acetic acid and vinyl acetate as acyl donors were also successfully used.