A computer program for analysis, simulation and optimization of asymmetric catalytic processes proceeding through two consecutive steps. Type 2: Sequential kinetic resolutions

Tetrahedron Asymmetry

Volumn 8, Issue 19, 1997, Pages 3263-3274

  Kroutil, W ^a   Kleewein, A ^a   Faber, K ^a  

^a GRAZ UNIVERSITY OF TECHNOLOGY   (Austria)

Author keywords

[No Author keywords available]

Indexed keywords

ARTICLE; CATALYSIS; CHEMICAL REACTION KINETICS; COMPUTER PROGRAM; DRUG SYNTHESIS; ENANTIOMER; PRIORITY JOURNAL;

EID: 0030773295     PISSN: 09574166     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0957-4166(97)00429-1     Document Type: Article

References (63)

1. Sih, C. J.; Wu, S.-H. Topics Stereochem. 1989, 19, 63-125.
2. Kagan H. B.; Fiaud, J. C. Topics Stereochem. 1988, 18, 249-330.
3. In biocatalytic reactions, the ratio of kinetic resolutions versus asymmetrization reactions is about 4:1 (Database Faber, 06-97, ∼8000 entries).
4. For a review see: Schoffers, E.; Golebiowski, A.; Johnson, C. R. Tetrahedron 1996, 52, 3769-3826.
5. Evaluation of an extensive list of materials available from the chiral pool reveals that from a total of 375 compounds, a majority of 255 is available from an unaffordable price-range of >1000 US$ per kg. Only 41 compounds are cheap (<100 US$/kg), 45 are affordable (100-250 US$/kg), and the remainder of 34 range from 250-1000 US$/kg. For a list of compounds see: Scott, J. W. Readily available chiral carbon fragments and their use in synthesis. In Asymmetric Synthesis Morrison, J. D.; Scott, J. W., Eds, Academic Press, London, 1984, vol. 4, pp. 1-226.
6. For recent monographs see: Roberts, S. M.; Turner, N. J.; Willetts, A. J.; Turner, M. K. Introduction to Biocatalysis using Enzymes and Micro-Organisms Cambridge University Press, Cambridge, 1995; Wong, C.-H.; Whitesides, G. M. Enzymes in Synthetic Organic Chemistry Pergamon, Oxford, 1994. For a textbook see: Faber, K. Biotransformations in Organic Chemistry 3rd edn, Springer, Heidelberg, 1997. For a manual see: Drauz, K.; Waldmann, H., Eds Enzymes in Organic Synthesis - a Comprehensive Handbook Verlag Chemie, Weinheim, 1995. For preparative procedures see: Roberts, S. M., Ed. Preparative Biotransformations Wiley, New York, 1993 and regular updates.
7. For recent monographs see: Roberts, S. M.; Turner, N. J.; Willetts, A. J.; Turner, M. K. Introduction to Biocatalysis using Enzymes and Micro-Organisms Cambridge University Press, Cambridge, 1995; Wong, C.-H.; Whitesides, G. M. Enzymes in Synthetic Organic Chemistry Pergamon, Oxford, 1994. For a textbook see: Faber, K. Biotransformations in Organic Chemistry 3rd edn, Springer, Heidelberg, 1997. For a manual see: Drauz, K.; Waldmann, H., Eds Enzymes in Organic Synthesis - a Comprehensive Handbook Verlag Chemie, Weinheim, 1995. For preparative procedures see: Roberts, S. M., Ed. Preparative Biotransformations Wiley, New York, 1993 and regular updates.
8. For recent monographs see: Roberts, S. M.; Turner, N. J.; Willetts, A. J.; Turner, M. K. Introduction to Biocatalysis using Enzymes and Micro-Organisms Cambridge University Press, Cambridge, 1995; Wong, C.-H.; Whitesides, G. M. Enzymes in Synthetic Organic Chemistry Pergamon, Oxford, 1994. For a textbook see: Faber, K. Biotransformations in Organic Chemistry 3rd edn, Springer, Heidelberg, 1997. For a manual see: Drauz, K.; Waldmann, H., Eds Enzymes in Organic Synthesis - a Comprehensive Handbook Verlag Chemie, Weinheim, 1995. For preparative procedures see: Roberts, S. M., Ed. Preparative Biotransformations Wiley, New York, 1993 and regular updates.
9. For recent monographs see: Roberts, S. M.; Turner, N. J.; Willetts, A. J.; Turner, M. K. Introduction to Biocatalysis using Enzymes and Micro-Organisms Cambridge University Press, Cambridge, 1995; Wong, C.-H.; Whitesides, G. M. Enzymes in Synthetic Organic Chemistry Pergamon, Oxford, 1994. For a textbook see: Faber, K. Biotransformations in Organic Chemistry 3rd edn, Springer, Heidelberg, 1997. For a manual see: Drauz, K.; Waldmann, H., Eds Enzymes in Organic Synthesis - a Comprehensive Handbook Verlag Chemie, Weinheim, 1995. For preparative procedures see: Roberts, S. M., Ed. Preparative Biotransformations Wiley, New York, 1993 and regular updates.
10. For recent monographs see: Roberts, S. M.; Turner, N. J.; Willetts, A. J.; Turner, M. K. Introduction to Biocatalysis using Enzymes and Micro-Organisms Cambridge University Press, Cambridge, 1995; Wong, C.-H.; Whitesides, G. M. Enzymes in Synthetic Organic Chemistry Pergamon, Oxford, 1994. For a textbook see: Faber, K. Biotransformations in Organic Chemistry 3rd edn, Springer, Heidelberg, 1997. For a manual see: Drauz, K.; Waldmann, H., Eds Enzymes in Organic Synthesis - a Comprehensive Handbook Verlag Chemie, Weinheim, 1995. For preparative procedures see: Roberts, S. M., Ed. Preparative Biotransformations Wiley, New York, 1993 and regular updates.
11. Chen, C-S.; Fujimoto, Y.; Girdaukas, G.; Sih, C. J. J. Am. Chem. Soc. 1982, 104, 7294-7299.
12. For a review see: Faber, K.; Ottolina, G.; Riva, S. Biocatalysis 1993, 8, 91-132.
13. In order to obtain material with very high e.e. from single-step kinetic resolutions showing moderate E-values, it has been suggested that the resolution is repeated by starting with enantiomerically enriched material obtained from the previous step. Although such 'repeated resolutions' will eventually lead to enantiopure material after a certain number of cycles, the chemical yield of the overall process would be drastically diminished. See: Guo, Z.-W. J. Org. Chem. 1993, 58, 5748-5752; Vänttinen, E.; Kanerva, L. T. Tetrahedron: Asymmetry 1997, 8, 923-933.
14. In order to obtain material with very high e.e. from single-step kinetic resolutions showing moderate E-values, it has been suggested that the resolution is repeated by starting with enantiomerically enriched material obtained from the previous step. Although such 'repeated resolutions' will eventually lead to enantiopure material after a certain number of cycles, the chemical yield of the overall process would be drastically diminished. See: Guo, Z.-W. J. Org. Chem. 1993, 58, 5748-5752; Vänttinen, E.; Kanerva, L. T. Tetrahedron: Asymmetry 1997, 8, 923-933.
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19. Faber, K.; Hönig, H.; Kleewein, A. (© 1995). Free shareware programs for the calculation of the Enantiomeric Ratio for irreversible kinetic resolution are available via Internet: 'Selectivity-Win-1.0' and 'Selectivity-Mac-1.0', http://www-orgc.tu-graz.ac.at. For an alternative program see: Anthonsen, H. W.; Hoff, B. H.; Anthonsen, T. Tetrahedron: Asymmetry 1996, 7, 2633-2638.
20. Faber, K.; Hönig, H.; Kleewein, A. (© 1995). Free shareware programs for the calculation of the Enantiomeric Ratio for irreversible kinetic resolution are available via Internet: 'Selectivity-Win-1.0' and 'Selectivity-Mac-1.0', http://www-orgc.tu-graz.ac.at. For an alternative program see: Anthonsen, H. W.; Hoff, B. H.; Anthonsen, T. Tetrahedron: Asymmetry 1996, 7, 2633-2638.
21. Kroutil, W.; Kleewein, A.; Faber, K. (© 1997). 'SeKiRe' stands for SEquential KInetic REsolution. Free shareware programs running under Windows 'SeKiRe-Win-1.0' and Macintosh 'SeKiRe-Mac-1.0' are available via Internet at or directly from the authors. A description of how to use the programs is given in the help-files which accompany the programs.
22. For the treatment of sequential reactions proceeding through an asymmetrization followed by a kinetic resolution (Type-1 systems), see the preceeding paper in this issue.
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32. Enzyme-catalyzed hydrolysis of a diester of a diol usually proceeds through two consecutive steps. On the contrary, diesters of dicarboxylates often produce only the monoester as the final product, because (at pH at around 7) the latter represents a highly polar species, which is not further hydrolyzed by most ester hydrolases. Chen, C.-S.; Fujimoto, Y.; Sih, C. J. J. Am. Chem. Soc. 1981, 103, 3580-3582; Ramos Tombo, G. M.; Schär, H.-B.; Zimmermann, W.; Ghisalba, O. Chimia 1985, 39, 313-315.
33. Enzyme-catalyzed hydrolysis of a diester of a diol usually proceeds through two consecutive steps. On the contrary, diesters of dicarboxylates often produce only the monoester as the final product, because (at pH at around 7) the latter represents a highly polar species, which is not further hydrolyzed by most ester hydrolases. Chen, C.-S.; Fujimoto, Y.; Sih, C. J. J. Am. Chem. Soc. 1981, 103, 3580-3582; Ramos Tombo, G. M.; Schär, H.-B.; Zimmermann, W.; Ghisalba, O. Chimia 1985, 39, 313-315.
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62. 2)/2 and represents the enantioselectivity that a hypothetical single-step resolution would need to yield the enantiomeric purity of the two-step process. See: Caron, G.; Kazlauskas, R. Tetrahedron: Asymmetry 1993, 4, 1995-2000.
63. For instance, this may be achieved by addition of organic cosolvents, causing the slow-down of one of the individual steps: Caron, G.; Kazlauskas, R. J. J. Org. Chem. 1991, 56, 7251-7256.