Desilylative elimination of the quinazolinone ring from 1-(4-oxoquinazolin-3-yl)-2-silylaziridines; preparation of an N–H aziridine in high enantiomeric excess by in situ nucleophilic addition to the derived azirine

Abstract

Aziridination of vinylsilanes PhCH=CHSiR₃ (R = Me, Et, Ph) with enantiopure 3-acetoxyaminoquinazolinone 11 gives the corresponding aziridines 12 [diastereoisomer ratio (dr) 10∶1], 18 (dr 13∶1) and 20 (dr 2∶1). Desilylative elimination of the quinazolinone from these aziridines by caesium fluoride in the presence of cyanide gives aziridine 14 by cyanide addition to the 3-unsubstituted azirine 13, produced in situ. Acylation of aziridine 14 with (S)-acetoxypropionyl chloride gives N-acylaziridine 16; the good correlation between the diastereoisomer ratios of aziridines 12, 18 and 20 and those of the N-acylaziridine 16 produced in each case suggests that intermediate azirine 13 is configurationally stable.

References

1. F. A. Davis, G. V. Reddy and H. Lui, J. Am. Chem. Soc., 1995, 117, 3651; L. Gentilucci, Y. Arijzen, L. Thijs and B. Zwanenberg, Tetrahedron Lett., 1995, 36, 4665.
2. R. S. Atkinson and B. J. Kelly, J. Chem. Soc., Chem. Commun., 1989, 836.
3. R. S. Atkinson, B. J. Kelly and J. Williams, Tetrahedron, 1992, 48, 7713.
4. R. S. Atkinson and B. J. Kelly, Tetrahedron Lett., 1989, 30, 2703.
5. Preliminary communication: R. S. Atkinson, M. P. Coogan and I. S. T. Lochrie, Chem. Commun., 1996, 789.
6. R. S. Atkinson and P. J. Williams, J. Chem. Soc., Perkin Trans. 2, 1996, 205.
7. R. S. Atkinson and B. J. Kelly, J. Chem. Soc., Perkin Trans. 1, 1989, 1657.
8. R. S. Atkinson, M. J. Grimshire and B. J. Kelly, Tetrahedron, 1989, 45, 2875.
9. Previously prepared in racemic form: Y. Gelas-Mialhe, G. Touraud and R. Vessière, Can. J. Chem., 1982, 60, 2830.
10. L. Thijs, J. J. M. Porskamp, A. A. W. M. Van Loon, M. P. W. Derks, R. W. Feenstra, J. Legters and B. Zwanenberg, Tetrahedron, 1990, 46, 2611.
11. B. Asboth and L. Polgar, Biochemistry, 1983, 22, 117.
12. D. W. Wooley, J. W. B. Hershey and H. A. Jodlawski, J. Org. Chem., 1963, 28, 2012.
13. R. S. Atkinson, M. P. Coogan and I. S. T. Lochrie, Tetrahedron Lett., 1996, 37, 5179.
14. R. S. Atkinson, E. Barker, P. J. Edwards and G. A. Thomson, J. Chem. Soc., Perkin Trans. 1, 1996, 1047.
15. J. J. Eisch and M. W. Foxton, J. Org. Chem., 1971, 36, 3520.
16. L. N. Lewis, K. G. Sy, G. L. Bryant and P. E. Donahue, Organometallics, 1991, 10, 3750.
17. M. A. Brook and A. Neuy, J. Org. Chem., 1990, 55, 3609.
18. S. A. Thomson, J. Med. Chem., 1986, 29, 104.
19. P. H. Lagriffoul, Z. Tadros, J. Taillades and A. Commeyras, J. Chem. Soc., Perkin Trans. 2, 1992, 1279.