A new benchmark for the non-enzymatic enantioselective acylation of amines: Use of a planar-chiral derivative of 4-pyrrolidinopyridine as the acylating agent

Chemical Communications

Volumn , Issue 2, 2000, Pages 119-120

  Ie, Yutaka ^a   Fu, Gregory C ^a  

^a MASSACHUSETTS INSTITUTE OF TECHNOLOGY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

AMINE; PYRIDINE DERIVATIVE;

ACYLATION; ARTICLE; CATALYST; CHEMICAL MODIFICATION; CHEMICAL REACTION; CHIRALITY; STEREOCHEMISTRY;

EID: 0034695460     PISSN: 13597345     EISSN: None     Source Type: Journal    
DOI: 10.1039/a908625k     Document Type: Article

References (27)

1. E. Vedejs, O. Daugulis and S. T. Diver, J. Org. Chem., 1996, 61, 430; E. Vedejs and O. Daugulis, J. Am. Chem. Soc., 1999, 121, 5813; T. Oriyama, Y. Hori, K. Imai and R. Sasaki, Tetrahedron Lett., 1996, 37, 8543; T. Sano, K. Imai, K. Ohashi and T. Oriyama, Chem. Lett., 1999, 265; T. Kawabata, M. Nagato, K. Takasu and K. Fuji, J. Am. Chem. Soc., 1997, 119, 3169; S. J. Miller, G. T. Copeland, N. Papaioannou, T. E. Horstmann and E. M. Ruel, J. Am. Chem. Soc., 1998, 110, 1629; G. T. Copeland, E. R. Jarvo and S. J. Miller, J. Org. Chem., 1998, 63, 6784.
2. E. Vedejs, O. Daugulis and S. T. Diver, J. Org. Chem., 1996, 61, 430; E. Vedejs and O. Daugulis, J. Am. Chem. Soc., 1999, 121, 5813; T. Oriyama, Y. Hori, K. Imai and R. Sasaki, Tetrahedron Lett., 1996, 37, 8543; T. Sano, K. Imai, K. Ohashi and T. Oriyama, Chem. Lett., 1999, 265; T. Kawabata, M. Nagato, K. Takasu and K. Fuji, J. Am. Chem. Soc., 1997, 119, 3169; S. J. Miller, G. T. Copeland, N. Papaioannou, T. E. Horstmann and E. M. Ruel, J. Am. Chem. Soc., 1998, 110, 1629; G. T. Copeland, E. R. Jarvo and S. J. Miller, J. Org. Chem., 1998, 63, 6784.
3. E. Vedejs, O. Daugulis and S. T. Diver, J. Org. Chem., 1996, 61, 430; E. Vedejs and O. Daugulis, J. Am. Chem. Soc., 1999, 121, 5813; T. Oriyama, Y. Hori, K. Imai and R. Sasaki, Tetrahedron Lett., 1996, 37, 8543; T. Sano, K. Imai, K. Ohashi and T. Oriyama, Chem. Lett., 1999, 265; T. Kawabata, M. Nagato, K. Takasu and K. Fuji, J. Am. Chem. Soc., 1997, 119, 3169; S. J. Miller, G. T. Copeland, N. Papaioannou, T. E. Horstmann and E. M. Ruel, J. Am. Chem. Soc., 1998, 110, 1629; G. T. Copeland, E. R. Jarvo and S. J. Miller, J. Org. Chem., 1998, 63, 6784.
4. E. Vedejs, O. Daugulis and S. T. Diver, J. Org. Chem., 1996, 61, 430; E. Vedejs and O. Daugulis, J. Am. Chem. Soc., 1999, 121, 5813; T. Oriyama, Y. Hori, K. Imai and R. Sasaki, Tetrahedron Lett., 1996, 37, 8543; T. Sano, K. Imai, K. Ohashi and T. Oriyama, Chem. Lett., 1999, 265; T. Kawabata, M. Nagato, K. Takasu and K. Fuji, J. Am. Chem. Soc., 1997, 119, 3169; S. J. Miller, G. T. Copeland, N. Papaioannou, T. E. Horstmann and E. M. Ruel, J. Am. Chem. Soc., 1998, 110, 1629; G. T. Copeland, E. R. Jarvo and S. J. Miller, J. Org. Chem., 1998, 63, 6784.
5. E. Vedejs, O. Daugulis and S. T. Diver, J. Org. Chem., 1996, 61, 430; E. Vedejs and O. Daugulis, J. Am. Chem. Soc., 1999, 121, 5813; T. Oriyama, Y. Hori, K. Imai and R. Sasaki, Tetrahedron Lett., 1996, 37, 8543; T. Sano, K. Imai, K. Ohashi and T. Oriyama, Chem. Lett., 1999, 265; T. Kawabata, M. Nagato, K. Takasu and K. Fuji, J. Am. Chem. Soc., 1997, 119, 3169; S. J. Miller, G. T. Copeland, N. Papaioannou, T. E. Horstmann and E. M. Ruel, J. Am. Chem. Soc., 1998, 110, 1629; G. T. Copeland, E. R. Jarvo and S. J. Miller, J. Org. Chem., 1998, 63, 6784.
6. E. Vedejs, O. Daugulis and S. T. Diver, J. Org. Chem., 1996, 61, 430; E. Vedejs and O. Daugulis, J. Am. Chem. Soc., 1999, 121, 5813; T. Oriyama, Y. Hori, K. Imai and R. Sasaki, Tetrahedron Lett., 1996, 37, 8543; T. Sano, K. Imai, K. Ohashi and T. Oriyama, Chem. Lett., 1999, 265; T. Kawabata, M. Nagato, K. Takasu and K. Fuji, J. Am. Chem. Soc., 1997, 119, 3169; S. J. Miller, G. T. Copeland, N. Papaioannou, T. E. Horstmann and E. M. Ruel, J. Am. Chem. Soc., 1998, 110, 1629; G. T. Copeland, E. R. Jarvo and S. J. Miller, J. Org. Chem., 1998, 63, 6784.
7. E. Vedejs, O. Daugulis and S. T. Diver, J. Org. Chem., 1996, 61, 430; E. Vedejs and O. Daugulis, J. Am. Chem. Soc., 1999, 121, 5813; T. Oriyama, Y. Hori, K. Imai and R. Sasaki, Tetrahedron Lett., 1996, 37, 8543; T. Sano, K. Imai, K. Ohashi and T. Oriyama, Chem. Lett., 1999, 265; T. Kawabata, M. Nagato, K. Takasu and K. Fuji, J. Am. Chem. Soc., 1997, 119, 3169; S. J. Miller, G. T. Copeland, N. Papaioannou, T. E. Horstmann and E. M. Ruel, J. Am. Chem. Soc., 1998, 110, 1629; G. T. Copeland, E. R. Jarvo and S. J. Miller, J. Org. Chem., 1998, 63, 6784.
8. (a) J. C. Ruble, H. A. Latham and G. C. Fu, J. Am. Chem. Soc., 1997, 119, 1492;
9. (b) J. C. Ruble, J. Tweddell and G. C. Fu, J. Org. Chem., 1998, 63, 2794;
10. C. E. Garrett, M. M.-C. Lo and G. C. Fu, J. Am. Chem. Soc., 1998, 120, 7479;
11. B. Tao, J. C. Ruble, D. A. Hoic and G. C. Fu, J. Am. Chem. Soc., 1999, 121, 5091.
12. Even enzymatic acylation of amines can be problematic. For a discussion and leading references, see: S. Takayama, S. T. Lee, S.-C. Hung and C. H. Wong, Chem. Commun., 1999, 127.
13. For a review of methods for the asymmetric synthesis of amines, see: A. Johansson, Contemp. Org. Synth., 1995, 2, 393; For leading references to applications of enantiopure amines, see: M. J. Burk, Y. M. Wang and J. R. Lee, J. Am. Chem. Soc., 1996, 118, 5142.
14. For a review of methods for the asymmetric synthesis of amines, see: A. Johansson, Contemp. Org. Synth., 1995, 2, 393; For leading references to applications of enantiopure amines, see: M. J. Burk, Y. M. Wang and J. R. Lee, J. Am. Chem. Soc., 1996, 118, 5142.
15. See: K. Kondo, T. Kurosaki and Y. Murakami, Synlett, 1998, 725 and references cited therein.
16. 6 For the enantioselective acylation of secondary alcohols, see ref. 2.
17. For other processes, see: J. C. Ruble and G. C. Fu, J. Org. Chem., 1996, 61, 7230; J. Liang, J. C. Ruble and G. C. Fu, J. Org. Chem., 1998, 63, 3154; J. C. Ruble and G. C. Fu, J. Am. Chem. Soc., 1998, 120, 11 532; B. L. Hodous, J. C. Ruble and G. C. Fu, J. Am. Chem. Soc., 1999, 121, 2637.
18. For other processes, see: J. C. Ruble and G. C. Fu, J. Org. Chem., 1996, 61, 7230; J. Liang, J. C. Ruble and G. C. Fu, J. Org. Chem., 1998, 63, 3154; J. C. Ruble and G. C. Fu, J. Am. Chem. Soc., 1998, 120, 11 532; B. L. Hodous, J. C. Ruble and G. C. Fu, J. Am. Chem. Soc., 1999, 121, 2637.
19. For other processes, see: J. C. Ruble and G. C. Fu, J. Org. Chem., 1996, 61, 7230; J. Liang, J. C. Ruble and G. C. Fu, J. Org. Chem., 1998, 63, 3154; J. C. Ruble and G. C. Fu, J. Am. Chem. Soc., 1998, 120, 11 532; B. L. Hodous, J. C. Ruble and G. C. Fu, J. Am. Chem. Soc., 1999, 121, 2637.
20. For other processes, see: J. C. Ruble and G. C. Fu, J. Org. Chem., 1996, 61, 7230; J. Liang, J. C. Ruble and G. C. Fu, J. Org. Chem., 1998, 63, 3154; J. C. Ruble and G. C. Fu, J. Am. Chem. Soc., 1998, 120, 11 532; B. L. Hodous, J. C. Ruble and G. C. Fu, J. Am. Chem. Soc., 1999, 121, 2637.
21. For example, with respect to the development of non-enzymatic methods for the kinetic resolution of alcohols, the discovery of effective stoichiometric reagents (D. A. Evans, J. C. Anderson and M. K. Taylor, Tetrahedron Lett., 1993, 34, 5563; E. Vedejs and X. Chen, J. Am. Chem. Soc., 1996, 118, 1809) preceded the discovery of effective catalysts (refs. 1 and 2).
22. For example, with respect to the development of non-enzymatic methods for the kinetic resolution of alcohols, the discovery of effective stoichiometric reagents (D. A. Evans, J. C. Anderson and M. K. Taylor, Tetrahedron Lett., 1993, 34, 5563; E. Vedejs and X. Chen, J. Am. Chem. Soc., 1996, 118, 1809) preceded the discovery of effective catalysts (refs. 1 and 2).
23. 2O preferentially acylates (R)-1-phenylethanol.
24. A preliminary study indicated that other N-acyl groups (e.g. pivaloyl) furnish lower enantioselectivity.
25. In contrast to our earlier papers on kinetic resolutions, in which we assessed stereoselection by focusing on the selectivity factor, in this work we have chosen to focus instead on the enantiomeric excess of the product. This is due to the fact that, because amine hydrochloride is the other product of these acylation reactions, calculation of a selectivity factor is not completely straightforward (the amine substrate is being 'consumed' both by acylation and by protonation).
26. H. B. Kagan and J. C. Fiaud, Top. Stereochem., 1988, 18, 249.
27. We have established that at the end of a reaction we can recover Ph-PPY* in 95% yield.