Anionically induced decomposition of 2-ethoxycarbonylprop-2-enyl peroxides

Abstract

Treatment of 2-ethoxycarbonylprop-2-enyl peroxides with potassium alkylperoxylate, the sodium enolate of diethyl malonate and a primary or secondary amine yields epoxides via a two-step process: (i) addition of the nucleophile to the acrylic unsaturated bond and (ii) intramolecular anionic substitution on the peroxidic bond.

References

1. see e.g. W. A. Kleschick, C. S. Lu and S. Thornburgh, Synthesis, 1990, 783; J. L. van der Baan, J. W. F. K. Barnick and F. Bickelhaupt, Synthesis, 1997, 897; M. Diaz and R. M. Ortuno, Tetrahedron: Asymmetry, 1995, 6, 1845; S. Saito, M. Takashi, T. Ishikawa and T. Morikawa, Tetrahedron Lett., 1991, 32, 667; R. Nouguier, M. P. Bertrand, P. Picon and P. Perfetti, Tetrahedron Lett., 1994, 35, 8171.
2. For a review, see G. Berti, Top. Stereochem., 1973, 7, 93.
3. R. R. Hiatt and V. G. K. Nair, Can. J. Chem., 1980, 58, 450.
4. E. Montaudon, F. Rakotomanana and B. Maillard, Bull. Soc. Chim. Fr., 1985, 198.
5. E. Montaudon, M. Agorrody, F. Rakotomanana and B. Maillard, Bull. Soc. Chim. Belg., 1987, 96, 769.
6. C. Navarro, M. Degueil-Castaing, D. Colombani and B. Maillard, Synlett, 1992, 587.
7. D. Colombani and B. Maillard, J. Chem. Soc., Perkin Trans. 2, 1994, 745.
8. H. S. Dang and B. P. Roberts, Tetrahedron Lett., 1992, 33, 4621; J. Chem. Soc., Perkin Trans. 1, 1993, 891.
9. B. Giese, Free Radicals in Organic Synthesis: Formation of Carbon-Carbon Bonds, Pergamon, Oxford, 1986, p. 29.
10. For a recent review, see P. Perlmutter, Conjugate Addition Reactions in Organic Synthesis, Pergamon, Oxford, 1992.
11. C. Navarro, M. Degueil-Castaing, D. Colombani and B. Maillard, Synth. Commun., 1993, 23, 1025.
12. N. C. Yang and R. A. Finnegan, J. Am. Chem. Soc., 1958, 80, 5845.
13. P. S. Engel and M. A. Schexnayder, J. Am. Chem. Soc., 1975, 97, 150.