Effective nonenzymatic kinetic resolution of (±)-trans-2-arylcyclohexanols using 3β-acetoxyetienic acid, DCC, and DMAP

Organic Process Research and Development

Volumn 7, Issue 4, 2003, Pages 583-584

  Matsugi, Masato ^a   Hagimoto, Yuri ^a   Nojima, Masatomo ^a   Kita, Yasuyuki ^a  

^a OSAKA UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

3BETA ACETOXYETIENIC ACID; 4 DIMETHYLAMINOPYRIDINE; ACID; DICYCLOHEXYLCARBODIIMIDE; HEXANOL; UNCLASSIFIED DRUG;

ARTICLE; ENANTIOMER; ESTERIFICATION; ISOMERISM; KINETICS; REACTION OPTIMIZATION; ROOM TEMPERATURE;

EID: 0043246691     PISSN: 10836160     EISSN: None     Source Type: Journal    
DOI: 10.1021/op0200928     Document Type: Article

References (31)

1. For reviews of the enzyme-catalyzed acyl transfer, see: Faber, K.; Riva, S. Synthesis 1992, 895. Carrea, G.; Riva, S. Angew. Chem., Int. Ed. 2000, 39, 2226.
2. For reviews of the enzyme-catalyzed acyl transfer, see: Faber, K.; Riva, S. Synthesis 1992, 895. Carrea, G.; Riva, S. Angew. Chem., Int. Ed. 2000, 39, 2226.
3. For reviews of the nonenzymatic kinetic resolution, see: Spivey, A. C.; Maddaford, A.; Redgrave, A. J. Organic Prep. Proced. Int. 2000, 32, 331. Somfai, P. Angew. Chem., Int. Ed. Engl. 1997, 36, 2731.
4. For reviews of the nonenzymatic kinetic resolution, see: Spivey, A. C.; Maddaford, A.; Redgrave, A. J. Organic Prep. Proced. Int. 2000, 32, 331. Somfai, P. Angew. Chem., Int. Ed. Engl. 1997, 36, 2731.
5. Recent examples and references therein: Clapham, B.; Cho, C. W.; Janda, K. D. J. Org. Chem. 2001, 66, 868. Sekar, G.; Nishiyama, H. J. Am. Chem. Soc. 2001, 123, 3603. Spivey, A. C.; Fekner, T.; Spey, S. E. J. Org. Chem. 2000, 65, 3154.
6. Recent examples and references therein: Clapham, B.; Cho, C. W.; Janda, K. D. J. Org. Chem. 2001, 66, 868. Sekar, G.; Nishiyama, H. J. Am. Chem. Soc. 2001, 123, 3603. Spivey, A. C.; Fekner, T.; Spey, S. E. J. Org. Chem. 2000, 65, 3154.
7. Recent examples and references therein: Clapham, B.; Cho, C. W.; Janda, K. D. J. Org. Chem. 2001, 66, 868. Sekar, G.; Nishiyama, H. J. Am. Chem. Soc. 2001, 123, 3603. Spivey, A. C.; Fekner, T.; Spey, S. E. J. Org. Chem. 2000, 65, 3154.
8. The selectivity factor was determined using the following equation: s = ln[(1 - C)(1 - ee)]/ln[(1 - C)(1 + ee)], where C = conversion. Kagan, H. B.; Fiaud, J. C. In Topics in Stereochemistry; Eliel, E. L., Ed.; Wiley & Sons: New York, 1988; Vol. 18, p 249.
9. The 3β-Acetoxyetienic acid can be easily prepared from the commercially available pregnenolone acetate (Aldrich; 59.7USD/25 g): Staunton, J.; Eisenbraun, E. J. Org. Synth. 1962, 42, 4. Djerassi, C.; Hart, P. A.; Warawa, E. J. J. Am. Chem. Soc. 1964, 86, 78.
10. The 3β-Acetoxyetienic acid can be easily prepared from the commercially available pregnenolone acetate (Aldrich; 59.7USD/25 g): Staunton, J.; Eisenbraun, E. J. Org. Synth. 1962, 42, 4. Djerassi, C.; Hart, P. A.; Warawa, E. J. J. Am. Chem. Soc. 1964, 86, 78.
11. Neises, B.; Steglich, W. Angew. Chem., Int. Ed. Engl. 1978, 17, 522.
12. The utilities of 2-arylcyclohexanols as chiral auxiliaries in synthesis: Whitesell, J. K. Chem. Rev. 1992, 92, 953.
13. For reviews of the CH/π interaction, see: Nishio, M.; Umezawa, Y.; Hirota, M.; Takeuchi, Y. Tetrahedron 1995, 51, 8665. Nishio, M.; Umezawa, Y.; Hirota, M. The CH/π Interaction; Wiley-VCH: New York, 1998.
14. For reviews of the CH/π interaction, see: Nishio, M.; Umezawa, Y.; Hirota, M.; Takeuchi, Y. Tetrahedron 1995, 51, 8665. Nishio, M.; Umezawa, Y.; Hirota, M. The CH/π Interaction; Wiley-VCH: New York, 1998.
15. Matsugi, M.; Itoh, K.; Nojima, M.; Hagimoto, Y.; Kita, Y. Tetrahedron Lett. 2001, 42, 6903. Matsugi, M.; Itoh, K.; Nojima, M.; Hagimoto, Y.; Kita, Y. Tetrahedron Lett. 2001, 42, 8019. Matsugi, M.; Nojima, M.; Hagimoto, Y.; Kita, Y. Tetrahedron Lett. 2001, 42, 8039.
16. Matsugi, M.; Itoh, K.; Nojima, M.; Hagimoto, Y.; Kita, Y. Tetrahedron Lett. 2001, 42, 6903. Matsugi, M.; Itoh, K.; Nojima, M.; Hagimoto, Y.; Kita, Y. Tetrahedron Lett. 2001, 42, 8019. Matsugi, M.; Nojima, M.; Hagimoto, Y.; Kita, Y. Tetrahedron Lett. 2001, 42, 8039.
17. Matsugi, M.; Itoh, K.; Nojima, M.; Hagimoto, Y.; Kita, Y. Tetrahedron Lett. 2001, 42, 6903. Matsugi, M.; Itoh, K.; Nojima, M.; Hagimoto, Y.; Kita, Y. Tetrahedron Lett. 2001, 42, 8019. Matsugi, M.; Nojima, M.; Hagimoto, Y.; Kita, Y. Tetrahedron Lett. 2001, 42, 8039.
18. The numbering positions on the steroid ring and hexane ring are respectively depicted by the positions of 3β-acetoxyetienic acid and 2-arylcyclohexanols before esterification for the simple discussion.
19. The kinetic resolution of racemic alcohols by using the DCC: Chinchilla, R.; Najera, C.; Yus, M.; Heumann, A. Tetrahedron: Asymmetry 1990, 1, 851. Chinchilla, R.; Najera, C.; Yus, M.; Heumann, A. Tetrahedron: Asymmetry 1991, 2, 101.
20. The kinetic resolution of racemic alcohols by using the DCC: Chinchilla, R.; Najera, C.; Yus, M.; Heumann, A. Tetrahedron: Asymmetry 1990, 1, 851. Chinchilla, R.; Najera, C.; Yus, M.; Heumann, A. Tetrahedron: Asymmetry 1991, 2, 101.
21. The kinetic resolution of racemic carboxylic acids by using the DCC: Camps, P.; Perez, F.; Soldevilla, N. Tetrahedron: Asymmetry 1997, 8, 1877. Calmes, M.; Glot, C.; Michel, T.; Rolland, M.; Martinez, J. Tetrahedron: Asymmetry 2000, 11, 737.
22. The kinetic resolution of racemic carboxylic acids by using the DCC: Camps, P.; Perez, F.; Soldevilla, N. Tetrahedron: Asymmetry 1997, 8, 1877. Calmes, M.; Glot, C.; Michel, T.; Rolland, M.; Martinez, J. Tetrahedron: Asymmetry 2000, 11, 737.
23. The chiral 3β-acetoxyetienic acid can be easily prepared from a commercially available pregnenolone acetate via the two steps; see: ref 5.
24. Bovey, F. A. Nuclear Magnetic Resonance Spectroscopy; Academic: New York, 1969; p 64.
25. D of the remaining 1i in the acylation process. Berti, G.; Macchia, B.; Macchia, F.; Monti, L. J. Org. Chem. 1968, 33, 4045.
26. Djerassi, C.; Hart, P. A.; Warawa, E. J. J. Am. Chem. Soc. 1964, 86, 78. Esser, P.; Buschmann, H.; Meyer-Stork, M.; Scharf, H.-D. Angew. Chem., Int. Ed. Engl. 1992, 31, 1190.
27. Djerassi, C.; Hart, P. A.; Warawa, E. J. J. Am. Chem. Soc. 1964, 86, 78. Esser, P.; Buschmann, H.; Meyer-Stork, M.; Scharf, H.-D. Angew. Chem., Int. Ed. Engl. 1992, 31, 1190.
28. D of the corresponding 1j after the removal of the steroid moiety, see: ref 16.
29. For recent reports on the participation of the CH/π attractive force, see Yamakawa, M.; Yamada, I.; Noyori, R. Angew. Chem., Int. Ed. 2001, 40, 2818. Noyori, R.; Yamakawa, M.; Hashiguchi, S. J. Org. Chem. 2001, 66, 7931.
30. For recent reports on the participation of the CH/π attractive force, see Yamakawa, M.; Yamada, I.; Noyori, R. Angew. Chem., Int. Ed. 2001, 40, 2818. Noyori, R.; Yamakawa, M.; Hashiguchi, S. J. Org. Chem. 2001, 66, 7931.
31. 2 = 8/1) to give 6.8 g of 3f (54.4%, 71% de) and 1.9 g of (1R, 2S)-1f (38.1%, 99% ee). The 3β-acetoxyetienic acid (457 mg, 3.8%) was recovered by the neutralization of the aqueous alkaline phase.