Abstract
The gas-solid halogenation and hydrohalogenation using microcrystalline cyclodextrin complexes are found to be efficient for production of the optical active halides of ethyltrans-cinnamate in moderate optical yields: On exposure to HBr at 20°C for 15–20 hr, the cinnamate in solid α- and β-cyclodextrin complexes yields ethyl R-(+)-3-bromo-3-phenylpropanoate in 46% e.e., and S-(−)-enantiomer in 31% e.e., respectively. No addition nor substitution products are obtained with HC1 vapor at 0–50°C for 15–65 hr. Bromination of the β-cyclodextrin complex results in the formation of optical active ethylerythro-2,3-dibromo-3-phenylpropanoate, while chlorination gives the optical active mixture oftrans andcis addition products, ethylerythro- andthreo-2,3-dichloro-3-phenylpropanoates in 60–80% yields. Mechanism of chiral induction in the present gas-solid reaction has been proposed on the basis of the crystal structure of the complex.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
K. Penzien and G. M. Schmidt,Angew. Chem. Int. Ed. Engl., 8. 608 (1969).
B. S. Green, M. Lahav, and D. Rabinovich,Accounts Chem. Res., 6. 191 (1979).
H. Nakanishi, Y. Tanaka, and H. Sakuraba, Paper presented at the 28 IUPAC. Congr. OR 162, Aug. 16–21, 1981, Vancouver, Canada; H. Sakuraba, Y. Tanaka, and H. Nakanishi, Paper presented at the 2nd Int. Kyoto Conf. New Aspect Org. Chem., C-30, Aug. 17–20, 1982, Kyoto, Japan; Y. Tanaka, H. Sakuraba, and H. Nakanishi,J. Chem. Soc., Chem Commun., 947 (1983).
M. L. Bender and M. Komiyama, ‘Cyclodextrin Chemistry’, Springer, Berlin, 1978.
J. D. Morrison and H. S. Mosher, ‘Asymmetric Organic Reactions’, p286, Prentice-Hall, Englewood Cliffs, N. J., 1971.
H. Erlenmeyer,Helv. Chem. Acta.,13, 731 (1930).
J. A. Riddick and W. B. Bunger, ‘Organic Solvents’, Wiley, New York, 1970.
O. Shimamura and M. Takahashi,Bull. Chem. Soc., Jpn.,22. 60 (1949).
K. Uekama, F. Hirayama, K. Esaki, and M. Inoue,Chem. Pharm. Bull.,27. 76 (1976).
M. B. Hursthouse, C. Z. Smith, M. Thornton-Pett, and J. H. P. Utley,J. Chem. Soc., Chem. Commun., 881 (1982).
R. E. Buckeles, E. A. Hausman, and N. G. Wheeler,J. Amer. Chem. Soc.,72. 2494 (1950).
Beilstein H 9. 518.
E. Hadjoudis, E. Kariv, and G. M. Schmidt,J. Chem. Soc., Perkin II. 1056 (1972).
H. Sakuraba, T. Nakai, and Y. Tanaka, unpublished data.
Beilstein E3 9. 2402.
M. L. Poutsma,J. Amer. Chem. Soc.,87. 2172 (1965).
M. M. Labes, H. W. Blakeslee, and J. E. Bloor,J. Amer. Chem. Soc.,87. 4251 (1965).
R. C. Fahey,J. Amer. Chem. Soc.,88. 4681 (1966).
R. C. Fahey and H. J. Schneider,J. Amer. Chem. Soc.,90, 4429 (1968).
E. S. Gould, ‘Mechanism and Structure in Organic Chemistry’, Holt, Rinehart, and Winston, New York, 1959.
M. J. S. Dewar and R. C. Fahey,J. Amer. Chem. Soc.,85, 2245, 2248 (1963).
W. R. Vaughan and R. Caple,J. Amer. Chem. Soc.,86, 4928 (1964).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Tanaka, Y., Sakuraba, H., Oka, Y. et al. Asymmetric halogenation and hydrohalogenation of ethyltrans-cinnamate in crystalline cyclodextrin complexes. Journal of Inclusion Phenomena 2, 841–850 (1984). https://doi.org/10.1007/BF00662253
Issue Date:
DOI: https://doi.org/10.1007/BF00662253