Nonenzymatic kinetic resolution of propargylic alcohols by a planar- chiral DMAP derivative: Crystallographic characterization of the acylated catalyst

Journal of the American Chemical Society

Volumn 121, Issue 21, 1999, Pages 5091-5092

  Tao, Beata ^a   Ruble, J Craig ^a   Hoic, Diego A ^a   Fu, Gregory C ^a  

^a MASSACHUSETTS INSTITUTE OF TECHNOLOGY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALCOHOL DERIVATIVE;

ACYLATION; ARTICLE; CATALYST; CHIRALITY; CRYSTALLOGRAPHY; ENANTIOMER; KINETICS; REACTION ANALYSIS; STEREOCHEMISTRY; STRUCTURE ANALYSIS;

EID: 0033516290     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja9906958     Document Type: Article

References (22)

1. Selectivity factor = (rate of fast-reacting enamiomer)/(rate of slow-reacting) enantiomer. For a review of kinetic resolution, see: Kagan, H. B.; Fiaud, J. C. Top. Stereochem. 1988, 18, 249-330.
2. Vedejs, E.; Daugulis, O.; Diver, S. T. J. Org. Chem. 1996, 61, 430-431. See also: Vedejs, E.; Chen, X. J. Am. Chem. Soc. 1996, 118, 1809- 1810 and Vedejs, E.; Chen, X. J. Am. Chem. Soc. 1997, 119, 2584-2585.
3. Vedejs, E.; Daugulis, O.; Diver, S. T. J. Org. Chem. 1996, 61, 430- 431. See also: Vedejs, E.; Chen, X. J. Am. Chem. Soc. 1996, 118, 1809-1810 and Vedejs, E.; Chen, X. J. Am. Chem. Soc. 1997, 119, 2584-2585.
4. Vedejs, E.; Daugulis, O.; Diver, S. T. J. Org. Chem. 1996, 61, 430- 431. See also: Vedejs, E.; Chen, X. J. Am. Chem. Soc. 1996, 118, 1809- 1810 and Vedejs, E.; Chen, X. J. Am. Chem. Soc. 1997, 119, 2584-2585.
5. Oriyama, T.; Hori, Y.; Imai, K.; Sasaki, R. Tetrahedron Lett. 1996, 37, 8543-8546.
6. Ruble, J. C.; Latham, H. A.; Fu, G. C. J. Am. Chem. Soc. 1997, 119, 1492-1493.
7. (b) Ruble, J. C.; Tweddell, J.; Fu, G. C. J. Org. Chem. 1998, 63, 2794-2795.
8. (c) Garrett, C. E.; Lo, M. M.-C.; Fu, G. C. J. Am. Chem. Soc. 1998, 120, 7479-7483.
9. Kawabata, T.; Nagato, M.; Takasu, K.; Fuji, K. J. Am. Chem. Soc. 1997, 119, 3169-3170.
10. (a) Miller, S. J.; Copeland, G. T.; Papaiannou, N.; Horstmann, T. E.; Ruel, E. M. J. Am. Chem. Soc. 1998, 110, 1629-1630.
11. (b) Copeland, G. T.; Jarvo, E. R.; Miller, S. J. J. Org. Chem. 1998, 63, 6784-6785.
12. For leading references to methods for preparing optically active propargylic alcohols, see: Matsumura, K.; Hashiguchi, S.; Ikariya, T.; Noyori, R. J. Am. Chem. Soc. 1997, 119, 8738-8739.
13. 3, the rate of acylation decreases, due to protonation of the catalyst by acetic acid.
14. 3 to the eluant). Analysis of the acetate by chiral GC revealed a 68.6% ee of the R enantiomer. The alcohol was converted into the acetate and then analyzed by chiral GC, which revealed a 96.0% ee of the S enantiomer. These ee values correspond to a selectivity factor of 20.2 at 58.3% conversion.
15. Notes: (a) The difference in selectivity factors that we report for the kinetic resolution of 4-phenyl-3-butyn-2-ol (Table 1, entry 5 and Table 2, entry 1: s = 17; Table 3, entry 1: s = 20) is due to a difference in the concentrations at which the reactions were run (1.0 vs 0.5 M in 4-phenyl-3-butyn-2-ol). (b) These reactions are not sensitive to small amounts of oxygen, moisture, or adventitious impurities-reactions run exposed to air with unpurified reagents provide selectivities identical to those observed for reactions run under an inert atmosphere with purified reagents. The catalyst can be recovered in nearly quantitative yield at the end of the reaction. (c) We observed lower selectivity when the kinetic resolutions were run in other solvents.
16. For reviews of the chemistry of DMAP, see: (a) Scriven, E. F. V. Chem. Soc. Rev. 1983, 12, 129-161. (b) Hassner, A.; Krepski, L. R.; Alexanian, V. Tetrahedron 1978, 34, 2069-2076. (c) Höfle, G.; Steglich, W.; Vorbrüggen, H. Angew. Chem., Int. Ed. Engl. 1978, 17, 569-583.
17. For reviews of the chemistry of DMAP, see: (a) Scriven, E. F. V. Chem. Soc. Rev. 1983, 12, 129-161. (b) Hassner, A.; Krepski, L. R.; Alexanian, V. Tetrahedron 1978, 34, 2069-2076. (c) Höfle, G.; Steglich, W.; Vorbrüggen, H. Angew. Chem., Int. Ed. Engl. 1978, 17, 569-583.
18. For reviews of the chemistry of DMAP, see: (a) Scriven, E. F. V. Chem. Soc. Rev. 1983, 12, 129-161. (b) Hassner, A.; Krepski, L. R.; Alexanian, V. Tetrahedron 1978, 34, 2069-2076. (c) Höfle, G.; Steglich, W.; Vorbrüggen, H. Angew. Chem., Int. Ed. Engl. 1978, 17, 569-583.
19. For a crystal structure of acetylated DMAP, see: Jones, P. G.; Linoh, K.; Blaschette, A. Z. Naturforsch. 1990, 45b, 267-270.
20. 6 salt).
21. 2) indicate that this rotamer is also the only detectable rotamer in solution.
22. 5 analogue of catalyst 1, which provides significantly lower selectivity factors in kinetic resolutions, the corresponding angle is 2°.