Lipase-catalyzed resolution of stereogenic centers in steroid side chains by transesterification in organic solvents: The case of a 26- hydroxycholesterol

Tetrahedron Asymmetry

Volumn 9, Issue 13, 1998, Pages 2193-2196

  Ferraboschi, Patrizia ^a   Rezaelahi, Shahrzad ^a   Verza, Elisa ^a   Santaniello, Enzo ^a  

^a UNIVERSITY OF MILAN   (Italy)

Author keywords

[No Author keywords available]

Indexed keywords

26 HYDROXYCHOLESTEROL; CHLOROFORM; ORGANIC SOLVENT; STEROID; TETRAHYDROFURAN; TRIACYLGLYCEROL LIPASE; VINYL ACETATE;

ARTICLE; BURKHOLDERIA CEPACIA; CATALYSIS; ESTERIFICATION; ISOMER; PRIORITY JOURNAL; STEREOCHEMISTRY;

EID: 0032479231     PISSN: 09574166     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0957-4166(98)00222-5     Document Type: Article

References (31)

1. (a) Faber, K.; Riva, S. Synthesis 1992, 895.
2. (b) Santaniello, E.; Ferraboschi, P.; Grisenti, P. Enzyme Microb. Technol. 1993, 15, 367.
3. (c) Fang, J.-M.; Wong, C.-H. Synlett 1994, 393.
4. (d) Carrea, G.; Ottolina, G.; Riva, S. Trends Biotechnol. 1995, 13, 63.
5. For a review, see: Riva, S. in Applied Biocatalysis, Blanch, H. W., Clark, D. S. Eds, M. Dekker, New York 1991, Vol. 1, 179-219.
6. (a) Njar, V. C. O.; Caspi, E. Tetrahedron Lett. 1987, 28, 6549.
7. (b) Riva, S.; Klibanov, A. M. J. Am. Chem. Soc. 1988, 110, 3291. For more recent examples, see:
8. (c) Adamczyk, M.; Chen, Y.-Y.; Fishpaugh, J. R.; Gebler, J. C. Tetrahedron: Asymmetry 1993, 4, 1467.
9. (d) Bertinotti, A.; Carrea, G.; Ottolina, G.; Riva, S. Tetrahedron 1994, 50, 13165.
10. (e) Baldessari, A.; Maier, M. S.; Gros, E. G. Tetrahedron Lett. 1995, 36, 4349.
11. (f) Baldessari, A.; Maier, M. S.; Gros, E. G. Helv. Chim. Acta 1997, 36, 4349.
12. Ferraboschi, P.; Molatore, A.; Verza, E.; Santaniello, E. Tetrahedron: Asymmetry 1996, 7, 1551.
13. The lipase was a generous gift from the italian subsidiary of Amano (Japan) through the kind interest of Mr. I. Gaudio (Mitsubishi Italia, Milano).
14. (a) Degueil-Castaing, M.; De Jeso, B.; Drouillard, S.; Maillard, B. Tetrahedron Lett. 1987, 28, 953.
15. (b) Wang, Y.-F.; Lalonde, J. J.; Momongan, M.; Bergbreiter, D. E.; Wong, C.-H. J. Am. Chem. Soc. 1988, 110, 7200.
16. Santaniello, E.; Ferraboschi, P.; Casati, S.; Manzocchi, Tetrahedron: Asymmetry 1995, 6, 1521 and references cited therein.
17. (a) Ferraboschi, P.; Grisenti, P.; Casati, R.; Fiecchi, A.; Santaniello, E. J. Chem. Soc., Perkins Trans. 1 1987, 1743.
18. (b) Ferraboschi, P.; Fiecchi, A.; Grisenti, P.; Santaniello, E. ibidem 1 1987, 1749.
19. Santaniello, E.; Ferraboschi, P.; Fiecchi, A.; Grisenti, P.; Manzocchi, A. J. Org. Chem. 1987, 117, 701.
20. Reaction of sodium phenylsulfinate with methyl vinyl ketone quantitatively afforded 4-phenylsulfonyl-2-butanone (Julia, M.; Badet, B. Bull. Soc. Chem. 1975, 1363). Ketalization (ethylene glycol in the presence of p-toluenesulfonic acid, 90% yield) afforded the required intermediate 3.
21. The 22-iododerivative 2 prepared starting from stigmasterol as described in Ref. 8b (50% yield) was treated with the phenylsulfone 3 and LDA (from butyl lithium and diisopropylamine) affording the intermediate 4 (87%). The phenylsulfonyl moiety was quantitatively removed by reaction with sodium amalgam (see Ref. 8b).
22. 4 in water/tetrahydrofuran (1/1) hydrolyzed both protecting groups (the i-steroid moiety and the ketal function) affording the 25-keto-27 norcholesterol 5 (95%).
23. Compound 5 was silylated (89%) with t-butyldimethyl silyl chloride and imidazole (Corey, E. J.; Venkateswarlu, A. J. Am. Chem. Soc. 1972, 94, 6190) and the 25-keto group was reacted with methoxy methyl triphenyl phosphonium chloride and LDA to afford the intermediate 6 (85%).
24. 4 in methanol, 79%).
25. A solution of 25R,S-1a (0.4 g, 1 mmol) in chloroform/tetrahydrofuran 1/2 (5.5 ml) and vinyl acetate (0.32 ml, 3.46 mmol) was added to the solid lipase (14 mg, 31.5 U/mg) with stirring at room temperature.
26. R 15.0 (alcohol) and 17.0 min (acetate).
27. 1H-NMR (500 MHz): the proton at position 3 showed a multiplet centered at 3.50 ppm and the protons at positon 26 a multiplet centered at 3.87 ppm.
28. 1H-NMR (500 MHz) analysis and the corresponding (R)-MTPA-esters were prepared. The derivative from (25R,S)-26-hydroxycholesterol showed a signal constituted by three groups of peaks: a pair of double doublets between 4.00-4.08 ppm and 4.18-4.25 ppm and a doublet at 4.13 ppm. In the case of MTPA ester of unreacted 1a the doublet at 4.13 ppm was not detectable and the same derivative prepared from the alcohol obtained by the hydrolysis of acetate 1b showed only the signal centered at 4.13 ppm.
29. Uomori, A.; Seo, S.; Sato, T.; Yoshimura, Y.; Takeda, K. J. Chem. Soc., Perkins Trans. 1 1987, 1713.
30. Ferraboschi, P.; Casati, S.; De Grandi, S.; Grisenti, P.; Santaniello, E. Biocatalysis 1994, 10, 279.
31. A recent interpretation of the enantiopreference of Pseudomonas cepacia lipase toward primary alcohols has been proposed; see: Weissfloch, A. N. E.; Kazlauskas, R. J. J. Org. Chem. 1995, 60, 6959.