Synthesis of novel chiral crown ethers derived from D-glucose and their application to an enantioselective Michael reaction

Abstract

New chiral monoaza-15-crown-5 derivatives anellated to methyl 4,6-di-O-butyl-α-D-glucopyranoside have been synthesized from 1 using the 4,6-O-benzylidene protecting group (removed by acetic acid) and 2,3-di-O-benzyl groups (removed by catalytic hydrogenolysis). The alkylation of the hydroxy groups in 1 and 5 with benzyl chloride and bis(2-chloroethyl) ether, respectively, were carried out in two-phase reactions using phase-transfer (PT) catalysts. These sugar-based crown ethers showed significant asymmetric induction as chiral PT catalysts in the Michael addition of 2-nitropropane to chalcone (90% ee). The substituent at the nitrogen atom of the crown ethers has a major influence on both the chemical yield and the enantioselectivity.

References

1. M. I. O'Donnell, Asymmetric Phase-transfer Reactions, in Catalytic Asymmetric Synthesis, ed. I. Ojima, VCH, New York, 1993, pp. 389–411 and references cited therein.
2. J. F. Stoddart, Top. Stereochem., 1987, 17, 207; J. M. Coteron, C. Vicent, C. Bosso and S. Penades, J. Am. Chem. Soc., 1993, 115, 10066.
3. R. Noyori, Asymmetric Catalysis in Organic Synthesis, John Wiley & Sons, New York, 1994, p. 241; M. Wills and H. Tye, J. Chem. Soc., Perkin Trans. 1, 1998, 3101; 1999, 1109.
4. M. Alonso-Lopez, J. Jimenez-Barbero, M. Martin-Lomas and S. Penades, Tetrahedron, 1988, 44, 1535.
5. D. A. H. van Maarschalkerwaart, N. P. Willard and U. K. Pandit, Tetrahedron, 1992, 48, 8825.
6. S. Aoki, S. Sasaki and K. Koga, Heterocycles, 1992, 33, 493.
7. P. P. Kanakamma, N. S. Mani, U. Maitra and V. Nair, J. Chem. Soc., Perkin Trans. 1, 1995, 2339.
8. L. Tőke, P. Bakó, Gy. M. Keserű, M. Albert and L. Fenichel, Tetrahedron, 1998, 54, 213 references cited therein.
9. P. Bakó and L. Tőke, J. Inclusion Phenom., 1995, 23, 195.
10. P. Bakó, Á. Szöllősy, P. Bombicz and L. Tőke, Synlett, 1997, 291.
11. P. Bakó, Á. Szöllősy, P. Bombicz and L. Tőke, Heteroatom Chem., 1997, 8, 333.
12. P. Bakó, K. Vízvárdi, S. Toppet, E. Van der Eycken, G. J. Hoornaert and L. Töke, Tetrahedron, 1998, 54, 14975.
13. P. Bakó, T. Kiss and L. Tőke, Tetrahedron Lett., 1997, 38, 7259.
14. J. S. Brimacombe, in Methods in Carbohydrate Chemistry, ed. R. L. Whistler, M. L. Wolfrom and J. N. Bemillar, Academic Press, New York, 1963, vol. 6. p. 376.
15. R. W. Jeanloz, in Methods in Carbohydrate Chemistry, ed. R. L. Whistler, M. L. Wolfrom and J. N. Bemillar, Academic Press, New York, 1962, vol. 1. p. 231.
16. (a) B. H. Lipshutz and M. C. Morey, J. Org Chem., 1981, 46, 2419; (b) N. J. Davis and L. Flitsch, J. Chem. Soc., Perkin Trans. 1, 1994, 359.
17. P. Di Cesare and B. Gross, Synth. Commun., 1979, 458.
18. F. Chavez and A. D. Sherry, J. Org. Chem., 1989, 54, 2990.
19. H. Pietraszkiewicz and J. Jurczak, Tetrahedron, 1984, 40, 2967.