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Asymmetric addition of methyl nitroacetate to crotonaldehyde catalyzed by chiral amines

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Abstract

The asymmetric Michael addition of methyl nitroacetate to crotonaldehyde catalyzed by chiral amines was carried out. The maximum chemical yield of diastereomeric products amounted to 95 %. The best asymmetric induction (42 % e.e.) was achieved in the case of catalysis by (S)-prolinol. The diastereomeric mixture was converted to a mixture of stereoisomeric 3-methyl-2-methoxycarbonylpyrrolidines. Absolute configurations of (2S,3S)-and (2R,3S)-isomers formed in excess were determined using GLC by comparison with authentic samples of racemic and optically pure forms of 3-methylproline.

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References

  1. 1.

    D. Seebach,Angew. Chem. Intern. Ed. Engl., 1990,29, 1320.

  2. 2.

    G. M. Coppola and H. F. Schuster, inAsymmetric Synthesis, John Wiley & Sons, New York, 1987.

  3. 3.

    H. B. Kagan,Bull. Soc. Chim. Fr. II., 1988, 846.

  4. 4.

    A. Corma, M. Iglezias, C. del Pino, and F. Sauch,J. Chem. Soc. Chem. Commun., 1991, 1253.

  5. 5.

    D. Muller, G. Umbricht, B. Weber, and A. Pfalts,Helv. Chim. Acta, 1991,74, 232.

  6. 6.

    R. O. Duthaler, A. Hafner, and M. Reidiker,Pure Appl. Chem., 1990,62, 631.

  7. 7.

    M. J. O'Donnell, W. D. Bennett, and S. Wu,J. Am. Chem. Soc., 1989,111, 2353.

  8. 8.

    K. B. Lipkomitz, M. W. Cavanangh, B. Baker, and M. J. O'Donnell,J. Org. Chem., 1991,56, 5181.

  9. 9.

    H. Hiemstra and H. Wynberg,J. Am. Chem. Soc., 1981,103, 417.

  10. 10.

    K. Suzuki, A. Ikegava, and T. Mukaiyama,Bull. Chim. Soc. Jpn., 1982,55, 3277.

  11. 11.

    M. T. Scipchandler,Synthesis, 1979, 666.

  12. 12.

    K. K. Babievskii, V. M. Belikov, and Yu. N. Belokon',Izv. Akad. Nauk SSSR, Ser. Khim., 1965, 1226 [Bull. Chem. Soc. USSR, Div. Chem. Sci., 1965,14, 1118 (Engl. Transl.)]

  13. 13.

    J. Kollonitsch, A. N. Scott, and C. A. Doldouras,J. Am. Chem. Soc., 1966,88, 3624.

  14. 14.

    N. Kornblum, R. K. Blackwood, and J. W. Powers,J. Am. Chem. Soc., 1957,79, 2507.

  15. 15.

    G. J. Nicholson, H. Frank, and E. Bayer,J. High Resolut. Chromatogr. & Chromatogr. Commun., 1979,28, 411.

  16. 16.

    Yu. N. Belokon', A. G. Belichev, V. F. Pavlov, E. B. Fedorova, V. A. Tsyryapkin, V. A. Bachmutov, and V. M. Belikov,J. Chem. Soc. Perkin Trans, 1, 1988, 2075.

  17. 17.

    H. Brunner, G. Riepl, and H. Weitzer,Angew. Chem. Int. Ed. Engl. (Suppl.), 1988, 445.

  18. 18.

    R. K. Dieter and M. Tokles,J. Am. Chem. Soc., 1978,109, 2040.

  19. 19.

    «ALDRICH» Catalog Handbook of Fine Chemicals, 1992–1993, 1080.

  20. 20.

    A. J. Gordon and R. A. Ford,The Chemist's Companion, Wiley-Intersci., New York—London—Sydney—Toronto, 1972.

  21. 21.

    Yu. N. Belokon', A. G. Bulychev, S. V. Vitt, Yu. T. Struchkov, A. S. Batsanov, T. V. Timofeeva, T. A. Tsyryapkin, M. G. Ryzhov, L. A. Lysova, V. I. Bachmutov, and V. M. Belikov,J. Am. Chem. Soc., 1985,105, 4252.

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Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1591–1595, September, 1993.

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Belokon', Y.N., Kochetkov, K.A., Churkina, T.D. et al. Asymmetric addition of methyl nitroacetate to crotonaldehyde catalyzed by chiral amines. Russ Chem Bull 42, 1525–1529 (1993). https://doi.org/10.1007/BF00699188

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Key words

  • asymmetric Michael addition
  • chiral amines
  • catalysis
  • methyl nitroacetate
  • crotonaldehyde
  • (S)-prolinol
  • 3-methylproline, enantiomeric excess