Conformational studies of N3-substituted [1,3,4]-oxadiazinan-2-ones

Journal of Organic Chemistry

Volumn 67, Issue 25, 2002, Pages 8871-8876

  Casper, David M ^a   Blackburn, Jennifer R ^a   Maroules, Christopher D ^a   Brady, Tana ^a   Esken, Joel M ^a   Ferrence, Gregory M ^a   Standard, Jean M ^a   Hitchcock, Shawn R ^a  

^a ILLINOIS STATE UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

STEREOELECTRONIC FACTORS;

CONFORMATIONS; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; X RAY CRYSTALLOGRAPHY;

ORGANIC COMPOUNDS;

[1,3,4]OXADIAZINAN 2 ONE DERIVATIVE; ACETYL[1,3,4]OXADIAZINAN 2 ONE; PHENYLACETYL[1,3,4]OXADIAZINAN 2 ONE; PROPIONYL[1,3,4]OXADIAZINAN 2 ONE; PSEUDOEPHEDRINE; UNCLASSIFIED DRUG;

ARTICLE; CARBON NUCLEAR MAGNETIC RESONANCE; CONFORMATIONAL TRANSITION; STOICHIOMETRY; STRUCTURE ANALYSIS; X RAY CRYSTALLOGRAPHY;

EID: 0037073889     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo020322g     Document Type: Article

References (24)

1. (a) Rosling, A.; Klika, K.; Fulop, F.; Sillanpaa, R.; Mattinen, J. Heterocycles 1999, 51, 2575.
2. (b) Rosling, A.; Hotokka, M.; Klika, K. D.; Fulop, F.; Sillanpaa, R.; Mattinen, J. Acta Chem. Scand. 1999, 53, 213.
3. (c) Rosling, A.; Fulop, F.; Sillanpaa, R.; Mattinen, J. Heterocycles 1997, 45, 95.
4. (a) Rosling, A.; Fulop, F.; Sillanpaa, R.; Mattinen, J. Heterocycles 1997, 45, 927.
5. (b) Riddell, F. G.; Kidd, A. J. J. Chem. Soc., Perkin. Trans. 2 1977,1816.
6. (c) Ferguson, I. J.; Katritzky, A. R.; Read, D. M. J. Chem. Soc., Perkin Trans. 2 1976, 1861.
7. (d) Dorman, L. J. Org. Chem. 1967, 32, 5.
8. Pyrazolidinones exhibit similar conformational properties in the context of lability at nitrogen. See: Sibi, M. P.; Liu, M. Org. Lett. 2001, 3, 4181.
9. (b) Sibi, M. P.; Venkatraman, L.; Liu, M.; Jasperse, C. P. J. Am. Chem. Soc. 2001, 123, 8444.
10. (a) The name formerly applied to these heterocycles is 3,4,5,6-tetrahydro-2H-1,3,4-oxadiazin-2-ones.
11. (b) Hitchcock, S. R.; Nora, G. P.; Casper, D. M.; Squire, M. D.; Maroules, C. D.; Ferrence, G. M.; Szczepura, L. F.; Standard, J. M. Tetrahedron 2001, 57, 9789.
12. Riddell and Katrizky independently observed similar conformational dynamics of the [1,3,4]-oxadiazinanes in their respective studies. See ref 2.
13. Trepanier prepared oxadiazinium salts earlier. Please see: (a) Trepanier, D. L.; Elbe, J. N.; Harris, G. H. J. Med. Chem. 1968, 11, 357. (b) Trepanier, D. L. Harris, J. N. U.S. patent 3,377,345, 1968; Chem. Abstr. 1969, 70, 78026c. We repeated the conditions using oxadiazinan-2-one 1 and obtained the oxadiazinium salt 4a in 78% yield.
14. Trepanier prepared oxadiazinium salts earlier. Please see: (a) Trepanier, D. L.; Elbe, J. N.; Harris, G. H. J. Med. Chem. 1968, 11, 357. (b) Trepanier, D. L. Harris, J. N. U.S. patent 3,377,345, 1968; Chem. Abstr. 1969, 70, 78026c. We repeated the conditions using oxadiazinan-2-one 1 and obtained the oxadiazinium salt 4a in 78% yield.
15. Attempts to acylate or alkylate the parent heterocycle 1 were either marginally successful (5%) or unsuccessful when n-BuLi was employed.
16. de Parrodi, C. A.; Clara-Sosa, A.; Pérez, L.; Quintero, L.; Marañón, V.; Tascano, R. A.; Aviña, J.; Rojas-Lima, S.; Juaristi, E. Tetrahedron: Asymmetry 2001, 12, 69.
17. Full details pertaining to data collection for 2a and 2b are collected in the Supporting Information along with tables of crystallographic details, atomic coordinates, bond lengths and angles, critical atom planes, torsional angles, anisotropic thermal parameters, and hydrogen atom parameters for 2a and 2b in CIF format.
18. For examples of conformations determined by repulsive interaction between the lone pair ofa carbonyl moiety and the lone pair of a nitrogen, see: (a) Weber, M.; Morgenstem, B.; Hegetschweiler, K.; Schmalle, H. W. Helv. Chim. Acta 2001, 84, 571. (b) Srivastava, A.; Srivastava, V.; Verma, S. M. Ind. J. Chem., B 1997, 36, 236.
19. For examples of conformations determined by repulsive interaction between the lone pair ofa carbonyl moiety and the lone pair of a nitrogen, see: (a) Weber, M.; Morgenstem, B.; Hegetschweiler, K.; Schmalle, H. W. Helv. Chim. Acta 2001, 84, 571. (b) Srivastava, A.; Srivastava, V.; Verma, S. M. Ind. J. Chem., B 1997, 36, 236.
20. 4-nitrogen thus giving rise to the parallel array.
21. Solvation phenomena must also be taken into account in arguments of the solution phase. We maintain that the conformation adopted in solution closely resembles that of the solid-state X-ray crystal structures based on observed signal broadening observed in oxadiazinan-2-ones 2d-k.
22. 4-methyl signal is still significantly broadened.
23. The aryl substituent is likely coplanar with the carbonyl. See: Leardini, R.; Lunazzi, L.; Mazzanti, A.; Nanni, D. J. Org. Chem. 2001, 66, 7879 and references therein.
24. Full details including choice of method via correlation to X-ray crystallographic data of 2a are collected in the Supporting Information.