Biocatalysis in Organic Synthesis 7. Enantioselective Transesterifications Catalyzed by an Acylase: Remarkable Influence of Remote Substitution and the Nature of the Solvent on the Selectivity

Synlett

Volumn 1996, Issue 5, 1996, Pages 449-451

  Ors, Marta ^a   Morcuende, Anabel ^a   Jiménez Vacas, M Isabel ^a   Valverde, Serafín ^a   Herradón, Bernardo ^a  

^a INSTITUTO DE QUÍMICA ORGÁNICA GENERAL   (Spain)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0002938694     PISSN: 09365214     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-1996-5455     Document Type: Article

References (25)

1. Part 6: Herradón, B.; Valverde, S. Synlett 1995, 599-602.
2. For some recent books, see: Wong, C.-H.; Whitesides, G. M. Enzymes in Synthetic Organic Chemistry; Pergamon Press, London, 1994. Faber, K. Biotransformations in Organic Chemistry, 2nd ed., Springer, Berlin, 1995. Enzymes Catalysis in Organic Synthesis. A Comprehensive Handbook, (Eds.: Drauz, K.; Waldmann, H.), VCH, Weinheim, 1995.
3. For some recent books, see: Wong, C.-H.; Whitesides, G. M. Enzymes in Synthetic Organic Chemistry; Pergamon Press, London, 1994. Faber, K. Biotransformations in Organic Chemistry, 2nd ed., Springer, Berlin, 1995. Enzymes Catalysis in Organic Synthesis. A Comprehensive Handbook, (Eds.: Drauz, K.; Waldmann, H.), VCH, Weinheim, 1995.
4. For some recent books, see: Wong, C.-H.; Whitesides, G. M. Enzymes in Synthetic Organic Chemistry; Pergamon Press, London, 1994. Faber, K. Biotransformations in Organic Chemistry, 2nd ed., Springer, Berlin, 1995. Enzymes Catalysis in Organic Synthesis. A Comprehensive Handbook, (Eds.: Drauz, K.; Waldmann, H.), VCH, Weinheim, 1995.
5. The advantages of this strategy ("experimental modulation of the selectivity") has been discussed elsewhere; see: Herradón, B.; Valverde, S. Tetrahedron: Asymmetry 1994, 5, 1479-1500; and references cited therein.
6. Chenault, H. K.; Dahmer, J.; Whitesides, G. M. J. Am. Chem. Soc. 1989, 111, 6354-6364.
7. a) For some recent synthetic applications of derivatives of 2-(hydroxymethyl)piperidine, see: Kozikowski, A. P.; Fauq, A. H.; Miller, J. H.; McKinney, M. Bioorg. Med. Chem. Lett. 1992, 2, 797-802. Gurjar, M. K.; Ghosh, L.; Syamala, M.; Jayasree, V. Tetrahedron Lett. 1994, 35, 8871-8872.
8. a) For some recent synthetic applications of derivatives of 2-(hydroxymethyl)piperidine, see: Kozikowski, A. P.; Fauq, A. H.; Miller, J. H.; McKinney, M. Bioorg. Med. Chem. Lett. 1992, 2, 797-802. Gurjar, M. K.; Ghosh, L.; Syamala, M.; Jayasree, V. Tetrahedron Lett. 1994, 35, 8871-8872.
9. b) Chiral derivatives of 2-(hydroxymethyl)piperidine are convenient building blocks for the EPC-synthesis of piperidine alkaloids, see: Strunz, G. M.; Findlay, J. A. The Alkaloids 1985, 26, 89-183.
10. c) Derivatives of 2-(hydroxymethyl)piperidine are precursors of the synthetically useful, but expensive, derivatives of both enantiomers of pipecolinic acid; for some recent synthetic applications of pipecolinic acid, see: Boger, D. L.; Chen, J. C. J. Am. Chem. Soc. 1993, 115, 11624-11625. Belshaw, P. J.; Meyer, S. D.; Johnson, D. D.; Romo, D.; Ikeda, Y.; Andrus, M.; Alberg, D. G.; Schultz, L. W.; Clardy, J.; Schreiber, S. L. Synlett 1994, 381-392. Nicolaou, K. C.; Piscopio, A. D.; Bertinato, P.; Chakraborty, T. K.; Minowa, N.; Koide, K.; Chem. Eur. J. 1995, 1, 318-333.
11. c) Derivatives of 2-(hydroxymethyl)piperidine are precursors of the synthetically useful, but expensive, derivatives of both enantiomers of pipecolinic acid; for some recent synthetic applications of pipecolinic acid, see: Boger, D. L.; Chen, J. C. J. Am. Chem. Soc. 1993, 115, 11624-11625. Belshaw, P. J.; Meyer, S. D.; Johnson, D. D.; Romo, D.; Ikeda, Y.; Andrus, M.; Alberg, D. G.; Schultz, L. W.; Clardy, J.; Schreiber, S. L. Synlett 1994, 381-392. Nicolaou, K. C.; Piscopio, A. D.; Bertinato, P.; Chakraborty, T. K.; Minowa, N.; Koide, K.; Chem. Eur. J. 1995, 1, 318-333.
12. c) Derivatives of 2-(hydroxymethyl)piperidine are precursors of the synthetically useful, but expensive, derivatives of both enantiomers of pipecolinic acid; for some recent synthetic applications of pipecolinic acid, see: Boger, D. L.; Chen, J. C. J. Am. Chem. Soc. 1993, 115, 11624-11625. Belshaw, P. J.; Meyer, S. D.; Johnson, D. D.; Romo, D.; Ikeda, Y.; Andrus, M.; Alberg, D. G.; Schultz, L. W.; Clardy, J.; Schreiber, S. L. Synlett 1994, 381-392. Nicolaou, K. C.; Piscopio, A. D.; Bertinato, P.; Chakraborty, T. K.; Minowa, N.; Koide, K.; Chem. Eur. J. 1995, 1, 318-333.
13. Chiral amino alcohol derivatives are useful chiral auxiliaries for asymmetric synthesis, see: Tillyer, R. D.; Boudreau, C.; Tschaen, D.; Dolling, U.-H.; Reider, P. J. Tetrahedron Lett. 1995, 36, 4337-4340; and references cited therein.
14. Usually the structural modifications of the substrate in enzyme-mediated transformations have been carried out near to the reacting center and/or the stereogenic center(s). The effect of remote substitution has not been sufficiently considered, although this kind of study can provide data on the structural features of the regions not too nearby the active center of the enzyme. For a paper dealing with remote substitution (although not so far as in the present paper), see: Toone, E. J.; Jones, J. B. Tetrahedron: Asymmetry 1991, 2, 1041-1052.
15. The starting materials (±)-1 have been prepared through microwave-promoted selective acylation of (±)-2-(hydroxymethyl)piperidine catalyzed by dibutyltin oxide. For a related procedure, see: Herradón, B.; Morcuende, A.; Valverde, S. Synlett 1995, 455-458.
16. 3, c = 0.61).
17. Sih, C. J.; Wu, S. H. Topics in Stereochemistry 1989, 19, 63-125.
18. a) Usually, molecules bearing sterically demanding groups are not substrates for many enzymes; for some examples, see: Zemlicka, J.; Craine, L. E.; Heeg, M.-J.; Oliver, J. P. J. Org. Chem. 1988, 53, 937-942. Naemura, K.; Takahashi, N; Chikamatsu, H. Chem. Lett. 1988, 1717-1720.
19. a) Usually, molecules bearing sterically demanding groups are not substrates for many enzymes; for some examples, see: Zemlicka, J.; Craine, L. E.; Heeg, M.-J.; Oliver, J. P. J. Org. Chem. 1988, 53, 937-942. Naemura, K.; Takahashi, N; Chikamatsu, H. Chem. Lett. 1988, 1717-1720.
20. b) On the other hand, when these molecules, bearing voluminous groups, are substrates of enzymes, highly selective transformations are achieved, see: Scilimati, A.; Ngooi, T. K.; Sih, C. J. Tetrahedron Lett. 1988, 29, 4927-4930. Kim, M.-J.; Choi, Y. K. J. Org. Chem. 1992, 57, 1605-7. Goergens, U.; Schneider, M. P. Tetrahedron: Asymmetry 1992, 3, 1149-1152.
21. b) On the other hand, when these molecules, bearing voluminous groups, are substrates of enzymes, highly selective transformations are achieved, see: Scilimati, A.; Ngooi, T. K.; Sih, C. J. Tetrahedron Lett. 1988, 29, 4927-4930. Kim, M.-J.; Choi, Y. K. J. Org. Chem. 1992, 57, 1605-7. Goergens, U.; Schneider, M. P. Tetrahedron: Asymmetry 1992, 3, 1149-1152.
22. b) On the other hand, when these molecules, bearing voluminous groups, are substrates of enzymes, highly selective transformations are achieved, see: Scilimati, A.; Ngooi, T. K.; Sih, C. J. Tetrahedron Lett. 1988, 29, 4927-4930. Kim, M.-J.; Choi, Y. K. J. Org. Chem. 1992, 57, 1605-7. Goergens, U.; Schneider, M. P. Tetrahedron: Asymmetry 1992, 3, 1149-1152.
23. 3 that some enzymes (such as the lipases from Pseudomonas species) are quite stable in polar solvents, such as pyridine, acetone and acetonitrile.
24. Toone, E. J.; Jones, J. B. Can. J. Chem. 1987, 65, 2722-2726. Asensio, G.; Andreu, C.; Marco, J. A. Tetrahedron Lett. 1991, 32, 4197-4198. Herradón, B. Unpublished results.
25. Toone, E. J.; Jones, J. B. Can. J. Chem. 1987, 65, 2722-2726. Asensio, G.; Andreu, C.; Marco, J. A. Tetrahedron Lett. 1991, 32, 4197-4198. Herradón, B. Unpublished results.